EP1928955A1 - Nouvelle composition a base d'emulsion de bitume - Google Patents

Nouvelle composition a base d'emulsion de bitume

Info

Publication number
EP1928955A1
EP1928955A1 EP06808182A EP06808182A EP1928955A1 EP 1928955 A1 EP1928955 A1 EP 1928955A1 EP 06808182 A EP06808182 A EP 06808182A EP 06808182 A EP06808182 A EP 06808182A EP 1928955 A1 EP1928955 A1 EP 1928955A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
bitumen
composition according
weight
cold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06808182A
Other languages
German (de)
English (en)
French (fr)
Inventor
Javier Hurtado Aznar
Didier Lesueur
Jean-Valery Martin
David Monin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Innophos Inc
Original Assignee
Eurovia SA
Innophos Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eurovia SA, Innophos Inc filed Critical Eurovia SA
Publication of EP1928955A1 publication Critical patent/EP1928955A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds

Definitions

  • the invention relates to a paving composition or coated oil based bitumen emulsion consisting of an amphoteric surfactant and this technique use for the manufacture of materials for new pavements, for reinforcing or maintenance of old pavements or their punctual repair.
  • Bitumen emulsions are used routinely in road application to various applications where they are spread either alone for example, of layers hooking, layers of impregnation and spot repairs (stitch in time, seals, sealing cracks) or in the presence of aggregates to make surface coatings or cold mixes.
  • Bitumen means a road bitumen or any bitumen-based composition optionally containing one or more polymer and / or one or more acid or base and / or one or more emulsifiers and / or one or more viscosifiers and / or one or more fluxes and / or one or more plasticizers and / or any other additives for adjusting the properties of the composition;
  • Bitumen emulsion means an aqueous dispersion of bitumen optionally containing one or more additives and / or one or more emulsifiers and / or one or more viscosifiers and / or one or more fluxing agents and / or one or more plasticizers and / or any other additives for adjusting the properties of the emulsion.
  • Bituminous coating means a mixture of aggregates sorted by size and a bitumen optionally comprising one or more additive (s), for example organic or inorganic fibers, rubber crumbs, possibly from the recycling of used tires, miscellaneous waste (cables, polyolefins, ...) and their mixtures in all proportions;
  • additive for example organic or inorganic fibers, rubber crumbs, possibly from the recycling of used tires, miscellaneous waste (cables, polyolefins, ...) and their mixtures in all proportions;
  • aggregates by means of aggregates of various origins, including aggregates from quarries or gravel pits, recycling products such as aggregates from the milling of old asphalt, the production waste, materials from the recycling of construction materials (demolition concrete, ...), dairy, shale, artificial aggregates and from all sources such as from bottom ash from incineration of household refuse (MSWI) as well as their mixtures in all proportions;
  • cold mixes any mixture obtained by mixing a bitumen and aggregates emulsion, dry or unsaturated, optionally in the presence of water added in addition to that of the emulsion and that naturally present in the aggregates, and additives which may be the same as those generally employed in the asphalt, as well as more specific additives designed in particular to control the breaking of the emulsion, such as switches that may be selected for example from acids or bases, mineral additives such as hydraulic cement (Portland cement, pozzolans, Sorel cements, ...), lime, or mineral salts as well as setting retarders which can also be mineral salts or organic compounds such as for example, acids, bases or surfactants, agents such as salts or their acid with inorganic phosphates, phosphonates and phosphinates and / or polyphosphates and / or organic.
  • Said cold mixes may for example be obtained by mixing in various proportions an emulsion of bitumen and a wet or dry granulate.
  • the mixture makes it possible to finally obtain between 0.1 and 30 parts by weight of bitumen per 100 parts of dry aggregate (ie 0.1-30 parts per cent of phr) and preferably between 2 and 15 phr according to the applications.
  • examples of “cold mix” are the “cold-poured mixes”, “grave emulsion”, the “cold or dense open coated”, the “cold bituminous concretes”, or “cold recycling”.
  • the cold mix is designed to support an average traffic of about 10 to more than 5,000 trucks per day, and for periods ranging from a few years to 30 years, according to its role and position in the floor ( wearing course, base layer, reprof ilage, reinforcement of an old floor).
  • ECFs will be understood here as all variants of this technology, for example Bituminous Grout (CB) also described in the SETRA note cited. They typically have, and not limited to, a maximum size of aggregate ranging between 2 and 20 mm, a mineral skeleton possibly having a discontinuity and residual bitumen contents between 4 and 12 ppc. - by cold recycling, the technical means to bitumen emulsion described in detail in various publications, for example the guide entitled “Recycling of Pavements,” published in 2003 by the Technical Committee 7/8 "Road pavements" of Permanent International Association of Road Congress (PIARC), based in Paris La Défense. SETRA the notes (Notes of Information Highways Dependencies No.
  • Cold mixes are generally considered to be inferior to so-called "hot mixes" where the bitumen is fluidized by an elevation of temperature to be then mixed with aggregates because of their lower mechanical properties, which essentially confined them to low traffic routes.
  • Cold mixes have recognized ecological advantages over their hot counterparts. They enable first of all to remove the drying step of the essential aggregates for the HMA which is a saving significant energy and more harm to the atmosphere that suppresses (dust and pollution associated with heating) . They are then used to remove smoke emissions related to heating the bitumen to the coating and spreading, reducing the nuisance both for workers and residents.
  • Cold mixes have scalable mechanical properties over time, due to the breaking of the emulsion, that is to say the transition from an initial state where the bitumen is dispersed as fine droplets in a phase aqueous (emulsion) to a final state where the bitumen constitutes a film coating the aggregates.
  • This does not only come from the presence of water to be evacuated, but also from the complex interactions between the emulsion and the granulate.
  • traffic reopening times can be extremely long to render impossible the use of these techniques for works that require to limit the closing time to the user.
  • breaking kinetics of emulsion should allow the implementation of coated and thus provide sufficient maneuverability to mix between the output of the mixer and when it is implemented on the roadway.
  • the turnaround time is largely dependent on the chosen manufacturing / implementation system. For example, it is typically between 30 seconds to 2 minutes for the ECF machines where the product leaves directly from the mixer installed on the self-supporting machine to directly feed the spreading device placed behind. It is several hours to cold mixes made Coating Plant installed far from the site spreading, transport being done by truck. The maneuverability time then corresponds to the transport time between the central and the implementation workshop.
  • a cold mix must therefore meet two antinomic objectives: a break sufficiently delayed to allow implementation, but then very fast to allow an opening to fast traffic.
  • Asphalt emulsions generally comprise between 50 and 72% by weight of bitumen that may optionally contain one or more additives and a complement of aqueous phase type that may optionally contain one or more emulsifiers and / or additives.
  • cationic emulsions that is to say obtained with an emulsifier comprising one or more ionic groups carrying a positive electric charge.
  • emulsifiers generally require working in an acidified medium at pH levels that can reach in a usual and nonlimiting manner, values of 1.5 to 3.
  • Anionic emulsions are also used, and are obtained with an emulsifying agent comprising one or more ionic group (s) carrying a negative electric charge. This generally requires working in a basic medium at pH values that can usually reach values of 10 to 12.
  • emulsifiers such as nonionic and amphoteric.
  • the nonionic emulsifiers do not have an ionic group and the amphoters have both cationic and anionic groups depending on the conditions.
  • These emulsifiers are used in cold mixes and their use is restricted to very specific applications that differ significantly from both the scope of the present invention and its composition field.
  • US 5,928,418 discloses paving compositions comprising a bitumen emulsion comprising itself a surfactant associated with a polyphenolic compound and a compound selected from anionic polymeric dispersants and hydrocarboxylic acids or their water-soluble salts, and a compound selected from saccharides , sugar or polyhydric alcohols.
  • US Patents 5,558,702, US5,667,576, US5,667, 577 and WO 96 / 30,446 describe emulsion / charge mixtures comprising fillers such as fibers, clays, lime, sand or mixtures thereof. components which exhibit high stability to storable then grout used for waterproofing work, eg garage or parking descents. Such preparations can not be confused with coated cold since they don 't have the typical proportions, are stored several months after manufacturing and are taken in times of the order of hours and are not required to contribute heavy traffic.
  • the present invention aims to solve the problems of formulations cold mixes described in the prior art by providing a formula emulsion enabling an increase in faster cohesion, which significantly reduces the time reopening to traffic while maintaining sufficient maneuverability.
  • the incorporation of a bitumen emulsion base of some amphoteric emulsifiers in the formulation of a cold mix provides excellent control of the rheological properties the mix, particularly its initial handling, ensuring easy implementation, followed by a rapid decision guaranteeing rapid opening to traffic.
  • a paving composition consisting of: i) from 0.5 to 30%, preferably from 2 to 15% by weight of a bitumen emulsion itself constituted: a. from 0.1 to 3%, preferably from 0.5 to 1.5% by weight, by weight, of an amphoteric surfactant chosen from the products of formula (I) or (II)
  • - R 1 represents a linear or branched, saturated or unsaturated aliphatic group having from 6 to 24 carbon atoms
  • - R 2 is a linear or branched, saturated or unsaturated aliphatic group having from 2 to 6 carbon atoms, at least one of these carbon atoms being optionally substituted by a hydroxyl group
  • R 3 and R 4 which may be identical or different, represent a linear or branched, saturated or unsaturated aliphatic group comprising
  • R 5 which is identical or different, is a saturated or unsaturated, linear or branched aliphatic group comprising from 1 to 6 carbon atoms, at least one of these carbon atoms being, if appropriate, substituted by a hydroxyl group; ;
  • Y " is a group SO ⁇ " or COO " ;
  • - Z is a group SU 3 'or COO "or OH; b 30 to 95%, preferably from 45 to 80% by weight of bitumen, and c water in sufficient quantity to complete the.. emulsion (QSP 100%), ii) from 70 to 99.5%, preferably from 85 to 98%, by weight of aggregates, and iii) from 0 to 20% by weight, preferably between 1 and 15% by weight . total water.
  • the total water is understood as the total content of water, including that already present in the emulsion, that already present in the aggregates and the optionally added (called a "water addition” or “water ' contribution').
  • a water addition or "water ' contribution').
  • radicals of synthetic origin may be mentioned: methyl, hydroxymethyl, ethyl, propyl, isopropyl, hydroxypropyl, propylene, isopropylene, butyl, isobutyl, pentyl, isopentyl , hexyl, heptyl, octyl, nonyl, decanoyl, dodecanoyl, isotridecyl, and naturally occurring radicals: capric, caprylic, lauric, myristic, palmitic, stearic, behenic, oleic, ricinole
  • R 1 represents a mixture of aliphatic radicals derived from coconut oil.
  • R2 represents a linear group at
  • R 3 and / or R 4 and / or R 5 represent a methyl or ethyl radical.
  • the amphoteric surfactant may be chosen from cocoamidopropyl betaine (CAS: 70851-07-9), cocoamidopropyl hydroxysultaine (CAS: 70851-08-0) or sodium cocoamphoacetate (CAS: 68650-39 -5).
  • the amphoteric surfactant of the bitumen emulsion may be a mixture of amphoteric surfactants whose Ri radicals are aliphatic radicals of plant origin (coconut, palm, olive) or animal origin.
  • the composition may further comprise additives.
  • additives those skilled in the art will be able to adjust the amounts of the various ingredients while respecting the proportions of emulsion of bitumen, aggregates and water stated above.
  • the composition may further comprise a retarder which advantageously may be a surfactant, particularly a surfactant corresponding to formulas (I) and / or (II).
  • a retarder which advantageously may be a surfactant, particularly a surfactant corresponding to formulas (I) and / or (II).
  • This composition makes it possible to dispense with the use of acids or bases in the formulation of emulsions, which prevents plant safety issues associated with their use and the risk of burns or corrosion associated with the use of acidic or basic emulsions.
  • This composition also has the advantage of being low in toxicity to humans and not very toxic for the environment.
  • composition can also be added to the emulsion any type of latex that is to say anionic or cationic latex for obtaining coated polymer modified, without destabilizing the emulsion.
  • the bitumen used in the emulsion may be any which road bitumen.
  • the bitumen emulsion may further contain any type of additive making it possible to regulate in the properties including the viscosity enhancers, regulators outlet or salts, e.g., calcium chloride, potassium , sodium or any other salt of calcium, potassium, sodium or magnesium.
  • Said emulsion may also be a bitumen emulsion, said bitumen being modified by a polymer, by an acid, by a base, by a filler, mineral or organic or by a surfactant, taken alone or in combination.
  • the skilled person will adjust the amounts of the various ingredients while respecting the proportions of surfactants and bitumen stated above.
  • polymer for example, and in an indicative and non-limiting manner, is meant the copolymers of styrene and butadiene in all proportions or copolymers of the same chemical family (isoprene, natural rubber, etc.), optionally crosslinked in situ, the copolymers of vinyl acetate and ethylene in all proportions, or the same category (butyl acetate, methyl, ... and polyolefins), the crumb rubber from used tires or any other polymer commonly used for the modification of bitumens as well as any mixture of these polymers.
  • the acid there may be mentioned for example, phosphoric acid and its derivatives, salts and esters, hydrochloric acid and any acid or combination of acid.
  • organic and inorganic bases such as, for example, polyamines, imidazolines, pyrolidines, sodium hydroxide, lime or potassium hydroxide.
  • inorganic or organic filler for example, cement, lime, silica or carbon black, organic or mineral fibers.
  • surfactant modifying the bitumen mention may be made of emulsifiers anionic, cationic, nonionic or amphoteric.
  • Said emulsion may be manufactured by any suitable method, in particular a colloid mill, a static mixer, or by phase inversion.
  • the invention also relates to the use of the composition in a mixture with aggregates for the preparation of cold mixes particularly for road application.
  • the invention relates to the use of the composition in the coated preparation of cold-cast (ECF), concrete bituminous cold (BBF) 1 "grave emulsion", "open or dense coated with cold ", or the cold recycling preparation.
  • the cold recycling in place is based on 100% milling residue from an old pavement, and containing between 0.5 and 3% bitumen emulsion.
  • cold mixes can be advantageously obtained by applying the invention.
  • asphalt for spot repair that would be manufactured either manually or by a mixer possibly mounted on a mobile system, just before their implementation itself manually or performed by a special machine .
  • the subject of the invention is also a cold-poured mix consisting of the composition according to the invention, said cold mix being able to be by way of non-limiting example a cold-cast mix (ECF), a cold bituminous concrete (BBF ), "serious-emulsion", “cold open or cold mix” or cold recycling.
  • ECF cold-cast mix
  • BBF cold bituminous concrete
  • SEBSF cold bituminous concrete
  • Example 1 Preparation of a cold-poured asphalt mix for a wearing course applicable either on a new roadway or in renovation of the surface properties of old roadways.
  • emulsion 1 a current emulsion passing the Spanish specifications ECL-2d, hereinafter referred to as "emulsion 1" is used to produce a cold-cast mix corresponding to an ECF of 0/6 granularity, standardized in Spain (Lechada Bituminosa Tipo 3 LB-3).
  • the granulate chosen comes from the quarry of San Felices en Haro (Rioja - Spain) and its granulometric curve, compared to that of the standardized spindle LB-3 is as follows:
  • This emulsion manufactured industrially by the Probisa at its factory Burgos, contains 62% of a Nynas bitumen of grade 70/100, 0.35% of a cationic surfactant (fatty polyamine Asfier 208 from Kao) and a amount of acid sufficient to obtain a pH of the emulsion of the order of 3.
  • a cationic surfactant fatty polyamine Asfier 208 from Kao
  • ECF 1 aqueous solution of fatty polyamine hydrochloride
  • Emulsion 1 (mass composition):
  • Emulsion 2 12.8 (ie residual bitumen 7.7)
  • ECF 2 and 3 based emulsions of the invention allow to obtain results equivalent to the reference formula (MS 1) for abrasion and initial fluidity time, and better for the cohesion Benedict, the threshold of 2 Nm being exceeded after 30 min, a gain of reopening to traffic of about 30 min compared with the reference.
  • Example 2 Preparation of another form of cold-poured mix wearing course applicable to both new floor or in renovation of surface properties of old pavements.
  • Emulsion 3 12.9 (ie residual bitumen 7.7)
  • MS 5 composition by mass: Sand 0/6 of the career of
  • Example 1 bitumen residue 7.7
  • the ECF were evaluated by applying formulation of testing in Spain: fluidity time measured manually, cohesion Benedict's Test according to EN 12274-4, performed 10, 30 and 60 min after mixing the constituents and resistance to the abrasion test according to EN 12274-5, after curing 20 hours, 6O 0 C of the specimen.
  • the results for the three formulas ECF above are summarized in the following Table:
  • Example 3 Preparation of another form of cold-poured mix wearing course applicable to both new floor or in renovation of surface properties of old pavements.
  • ECF 6 mass composition: Sand 0/6 of the Bureba quarry (Burgos - Spain) 100,00
  • ECF was evaluated by the application formulation trials in Spain: fluidity time measured manually, Benedict cohesion according to EN 12274-4 test, carried out 10, 30 and 60 min after mixing the constituents and resistance to abrasion according to the test EN 12274-5, after curing 20 hours, 6O 0 C of the test piece.
  • the results obtained, compared with those of ECFs 1 and 5 of the examples above, are given in the following Table.
  • Example 4 Preparation of a Coated Recycled Cold usable as a base layer.
  • a reference emulsion was manufactured with an Asfier 218 commercial emulsifier supplied by Kao, and a bitumen from the Petrogal refinery in Sines, Portugal.
  • This emulsion was compared with the emulsions 4 and 5, made according to the invention, the emulsion 4 with another emulsifier according to the invention, a cocoamphoacetate (CAS: 68650-39-5), and the emulsion being carried out 5 with the emulsifier cocoamidopropyl betaine presented in example 1.
  • Emulsion 4 (mass composition):
  • Emulsion 5 (mass composition):
  • Emulsion 6 (mass composition):
  • the aggregate comprises 3.6 pph of old asphalt.
  • the particle size distribution of the crude milling aggregate was as follows:
  • the aggregate is mixed using a laboratory mixer with 3.3 pph (relative to dry milled) emulsion with a total water content of 4.5 phr and breaker (cement) up to 0.5 ppc to obtain forms of recycled coated following:
  • Coated 2 aggregate 100 mass parts emulsion 4 3, 3 breaker (cement) 0, 5 water supply 2, 0
  • Coated 3 aggregate 100 mass parts emulsion 5 2, 5 breaker (cement) 0, 5 water supply 2, 0
  • mixes according to the invention have a compressive strength greater than the reference after 1 day demonstrating a faster cohesion increase.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Road Paving Structures (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Road Repair (AREA)
EP06808182A 2005-09-22 2006-09-21 Nouvelle composition a base d'emulsion de bitume Withdrawn EP1928955A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0509695A FR2890953B1 (fr) 2005-09-22 2005-09-22 Nouvelle composition a base d'emulsion de bitume.
PCT/FR2006/002161 WO2007034081A1 (fr) 2005-09-22 2006-09-21 Nouvelle composition a base d'emulsion de bitume

Publications (1)

Publication Number Publication Date
EP1928955A1 true EP1928955A1 (fr) 2008-06-11

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Country Status (9)

Country Link
US (1) US7767015B2 (enrdf_load_stackoverflow)
EP (1) EP1928955A1 (enrdf_load_stackoverflow)
JP (1) JP4991728B2 (enrdf_load_stackoverflow)
CN (1) CN101313031B (enrdf_load_stackoverflow)
BR (1) BRPI0616277A2 (enrdf_load_stackoverflow)
CA (1) CA2623452C (enrdf_load_stackoverflow)
FR (1) FR2890953B1 (enrdf_load_stackoverflow)
UA (1) UA95462C2 (enrdf_load_stackoverflow)
WO (1) WO2007034081A1 (enrdf_load_stackoverflow)

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GAYLE KING ET AL: "POLYMER MODIFIED ASPHALT EMULSIONS Composition, Uses, and Specifications for Surface Treatments, FHWA-CFL/TD-12-004", 1 January 2012 (2012-01-01), pages 1 - 170, XP055119693, Retrieved from the Internet <URL:http://www.cflhd.gov/programs/techDevelopment/pavement/polymer/documents/02_Polymer_Modified_Asphalt_Emulsions_main_report.pdf> [retrieved on 20140523] *
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See also references of WO2007034081A1 *

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WO2007034081A1 (fr) 2007-03-29
CN101313031B (zh) 2014-05-14
FR2890953A1 (fr) 2007-03-23
CA2623452C (fr) 2014-09-02
US20090064898A1 (en) 2009-03-12
BRPI0616277A2 (pt) 2011-06-14
FR2890953B1 (fr) 2010-09-17
US7767015B2 (en) 2010-08-03
JP4991728B2 (ja) 2012-08-01
CA2623452A1 (fr) 2007-03-29
CN101313031A (zh) 2008-11-26
JP2009509073A (ja) 2009-03-05
UA95462C2 (uk) 2011-08-10

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