EP2935442A1 - Bituminous binder composition for producing surfacing materials at low temperatures - Google Patents

Bituminous binder composition for producing surfacing materials at low temperatures

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Publication number
EP2935442A1
EP2935442A1 EP13814100.7A EP13814100A EP2935442A1 EP 2935442 A1 EP2935442 A1 EP 2935442A1 EP 13814100 A EP13814100 A EP 13814100A EP 2935442 A1 EP2935442 A1 EP 2935442A1
Authority
EP
European Patent Office
Prior art keywords
binder composition
bituminous binder
additive
bituminous
temperature
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Withdrawn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
EP13814100.7A
Other languages
German (de)
French (fr)
Inventor
Carole RUOT
Romuald Botel
Alexandre CROC
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.)
TotalEnergies Marketing Services SA
Original Assignee
Total Marketing Services SA
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 Total Marketing Services SA filed Critical Total Marketing Services SA
Publication of EP2935442A1 publication Critical patent/EP2935442A1/en
Withdrawn legal-status Critical Current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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • 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
    • C08L2555/20—Mixtures of bitumen and aggregate defined by their production temperatures, e.g. production of asphalt for road or pavement applications
    • 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
    • C08L2555/50—Inorganic non-macromolecular ingredients
    • C08L2555/52—Aggregate, e.g. crushed stone, sand, gravel or cement
    • 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
    • C08L2555/60—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye

Definitions

  • the present invention relates to an additivated bituminous binder composition comprising at least one bitumen and at least one long-chain alkylthiol additive making it possible to reduce the temperatures of manufacture, of implementation, of compaction of the mixes and to reduce the mixing time and / or or to increase the workability of said mixes.
  • the invention also relates to the mixes obtained from said bituminous binder composition additive with long-chain alkylthiol.
  • the invention also relates to processes for the preparation at low temperatures of the mixes obtained from said bituminous binder composition additivated with the long-chain alkylthiol.
  • the invention further relates to the use of the long chain alkylthiol in a bituminous binder composition and the use of said bituminous binder composition additive composition with the long chain alkylthiol, for manufacturing at lower temperatures and at lower temperatures. mixing time of the mixes more manageable.
  • the invention also relates to the use of these mixes for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, floors, waterproofing buildings or structures, in particularly in road applications for the manufacture of foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
  • bituminous coating is meant a mixture of a bituminous binder composition with aggregates and optionally mineral fillers.
  • the aggregates are inorganic and / or synthetic aggregates, in particular recycling mills with dimensions greater than 2 mm, preferably between 2 mm and 20 mm, and the mineral fillers consist of fines (particles smaller than 0.063 mm in size). ), sand (particles of dimensions between 0.063 mm and 2 mm) and possibly chippings (particles larger than 2 mm, preferably between 2 mm and 4 mm).
  • the term granulate represents a granulate meeting the requirements of a road use. These aggregates are preferably derived from the crushing of massive rocks or alluvial rocks.
  • Aggregates are therefore a granular material used in construction.
  • a granulate can be natural, artificial or recycled.
  • natural granulate designates a granulate having not undergone any deformation other than mechanical.
  • artificial granulate refers to a granulate of mineral origin resulting from an industrial process including thermal or other transformations.
  • recycled granulate refers to a granulate obtained by treatment of an inorganic material previously used in the construction.
  • the aggregates used are road aggregates, meeting the relevant standards: NF EN 13043 in Europe and ASTM C33 in the United States of America.
  • the granular classes (d / D) of the constituents of these mixes that are the subject of the series of French product standards NF P98-130 to NF P98-141 that can be used according to the invention are the following: 0/2 (sand) , 0/4, 2/4 (chippings), 0 / 6.3, 2 / 6.3 and 4 / 6.3. These granular classes are understood in the sense of the standard XP PI 8-540, replaced today by the standard XP P18-545.
  • Asphalt mixes are used to make roads and are compacted with rollers when they are put in place.
  • the preparation of hot mixes comprises several steps.
  • the first step consists in mixing the bituminous binder composition with aggregates at a temperature called manufacturing temperature or coating temperature.
  • the bituminous binder composition / aggregate mixture or the bituminous binder composition / filler mixture is then spread at a so-called processing temperature.
  • the manufacturing temperature (or coating temperature) and implementation are between 160 ° C and 180 ° C
  • the compacting temperature is between 120 ° C and 150 ° C.
  • bitumen emulsions dispersions of bitumen in water.
  • the bitumen emulsions are prepared at temperatures below 100 ° C, but require the use of water and are mainly used for the manufacture of low to medium-stressed pavements because the mechanical performances obtained by these so-called “cold” techniques are generally indented when compared to so-called “hot” techniques.
  • the patent application WO2007135097 describes the use of a combination of two additives in a binder composition to reduce the temperature of manufacture and / or implementation of a bituminous product.
  • the first additive is a macro-molecular compound chosen from natural resins of vegetable origin or hydrocarbon waxes.
  • the second additive is a fatty acid derivative selected from the group consisting of fatty acid diesters and fatty acid ethers.
  • the application WO200906295 describes the use of a combination of additives for preparing warm mixes.
  • the additive combination comprises a surfactant and rheology modifier comprising a wax and a resin.
  • Patent application EP2192158 describes the use of at least one fatty acid triglyceride in a bituminous binder composition to reduce the hot mix production temperature.
  • EP2062941 describes the use of at least 10% by weight of glycerol in a bituminous binder composition to reduce the temperature of manufacture of hot mixes.
  • bitumen emulsion using a cold technique, a bitumen emulsion is used, the bituminous binder composition being additivated by a reaction product between a polyalkylene polyamine and an alkenylsucin anhydride and a polyolefin resin. carrying carboxyl groups and having an acid number of between 5 and 100 mg KOH / g. This mixture makes it possible to prepare improved bitumen emulsions.
  • the patent application FR2965271 describes the use of a succinic anhydride or succinimide additive in a bituminous binder composition to reduce the temperature of manufacture, implementation and / or compaction of warm mixes.
  • the applicant company has sought to find an alternative additive to existing additives, to reduce the manufacturing temperature, implementation and compaction of the mix while improving the mixing times and / or the workability of said mixes.
  • this additive is an alkylthiol of general formula (1) C n H 2n + i-SH, which has the advantage that it can be used alone and not in admixture or combination with other additives, such as c is the case in the prior art.
  • the main objective of the present invention is therefore to provide a process for preparing asphalt at lower temperatures, in order to reduce energy consumption, reduce the discharge of flue gases and reduce smoke emissions.
  • Another object of the present invention is to provide a process for preparing asphalt at lower temperatures, which is economical because implementing a low additive content.
  • Another object of the present invention is to provide a process for the preparation of asphalt at lower temperatures, in which the properties of the additive binder composition are not changed or little modified compared to the non-additive base bitumen. Thus properties such as consistency (penetrability, Ball and Ring temperature) or viscosity of the additive binder composition should not be changed.
  • Another object of the present invention is to provide a process for the preparation of asphalt at lower temperatures, to ensure good adhesiveness of the bituminous binder composition additive / aggregates and allowing a low stripping.
  • Another object of the present invention is to provide a method for preparing asphalt at lower temperatures which is anhydrous.
  • Another object of the present invention is to provide a process for the preparation of mixes at lower temperatures, the mixes obtained by said process having equivalent or improved mechanical properties compared to conventional mixes, conventionally manufactured from known processes at higher temperatures. high temperatures.
  • one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to stripping.
  • one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to rutting.
  • one of the objectives of the present invention is to provide a warm mix manufactured at lower temperatures, having a good modulus of rigidity.
  • the invention relates to a bituminous binder composition
  • a bituminous binder composition comprising at least one bitumen and at least one alkylthiol additive of general formula (1) C n H2 n + 1-SH wherein n represents an integer ranging from 18 to 110.
  • the invention also relates to a bituminous binder composition comprising from 0.1 to 20% by weight of alkylthiol additive of formula (1), based on the total weight of the bituminous binder composition.
  • the invention also relates to a bituminous binder composition further comprising a polymer selected from elastomers, plastomers and mixtures thereof.
  • the invention also relates to a bituminous binder composition further comprising a crosslinking agent.
  • the invention also relates to a process for preparing a bituminous binder composition as described above comprising mixing the alkylthiol additive of general formula (1) and bitumen at a temperature of between 100 ° C. and 190 ° C. vs.
  • the invention also relates to a process for preparing a bituminous binder composition as described above further comprising a polymer chosen from elastomers, plastomers and mixtures thereof, said process comprising the following steps:
  • the invention also relates to a bituminous mix comprising a bituminous binder composition and aggregates optionally comprising fines, sand, chippings.
  • the invention also relates to a process for the preparation of a bituminous mix comprising mixing the bituminous binder composition as defined above with aggregates, in which the coating temperature is between 100 ° C. and 150 ° C. .
  • the invention also relates to a process for preparing a bituminous mix in which the bituminous binder composition and the aggregates are both at a temperature of between 100 ° C and 150 ° C.
  • the invention also relates to a process for the preparation of a bituminous mix in which the application temperature during spreading of the bituminous binder / aggregate composition mixture is between 80 ° C. and 150 ° C.
  • the invention also relates to a process for preparing a bituminous mix in which the compacting temperature of the spilled mixture is between 70 ° C. and 140 ° C.
  • the invention also relates to a process for preparing a bituminous mix in which the mixing time is between 2 seconds and 5 minutes.
  • the invention also relates to the use of an alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer varying from 18 to 110, in a bituminous binder composition to reduce the temperature manufacture, implementation and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
  • an alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer varying from 18 to 110, in a bituminous binder composition to reduce the temperature manufacture, implementation and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
  • the invention also relates to the use of a bituminous binder composition as defined above for reducing the temperatures of manufacture, implementation and / or compaction of a bituminous mix and / or improving the mixing time. and / or the workability of said mix.
  • the invention also relates to the use of an asphalt mix for the manufacture of road, pavement, sidewalk, road, urban development, floor, building or building waterproofing, particularly for the manufacture in road application, foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
  • the bituminous binder composition comprises at least one bitumen and at least one alkylthiol additive of the general formula (1) C n H 2n + i-SH wherein n represents an integer ranging from 18 to 110.
  • the alkylthiol additive comprises a saturated hydrocarbon chain, linear or branched, of at least 18 carbon atoms.
  • the saturated hydrocarbon chain of the alkylthiol is linear.
  • the saturated hydrocarbon chain of alkylthiol has the general formula C n H 2n + 1 , where n represents an integer greater than or equal to 18, preferably ranging from 18 to 110, preferably ranging from 18 to 90, preferably ranging from 18 to 50, preferably ranging from 18 to 40 and preferably ranging from 18 to 30.
  • C30H61 SH is for example marketed by Connect Marketing GmbH.
  • bituminous binder composition comprises at least one bitumen.
  • This bitumen is taken alone or mixed.
  • bitumens that can be used according to the invention, mention may be made first of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands.
  • Bitumens according to the invention also include bitumens derived from the refining of crude oil. Bitumens come from the atmospheric and / or vacuum distillation of oil. These bitumens can be optionally blown, vis-reduced and / or deasphalted. The different bitumens obtained by the refining processes can be combined with one another to obtain the best technical compromise. Bitumen can also be a recycling bitumen.
  • the bitumens may be hard grade or soft grade bitumens.
  • the bitumens according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, of between 5 and 200 1/10 mm, of preferably between 10 and 100 1/10 mm, more preferably between 20 and 60 1/10 mm, even more preferably between 30 and 50 1/10 mm.
  • the additive bituminous binder composition according to the invention comprises from 0.1 to 20% by weight of alkylthiol additive of general formula (1), relative to the total mass of the bituminous binder composition, preferably from 0.5 at 10% by weight, more preferably from 0.7 to 5% by weight, more preferably from 0.8 to 2% by weight.
  • bituminous binder composition it is preferred to use the smallest amount of additive possible, for economic reasons, but also technical. Indeed, if the additive is present in a significant amount in the bituminous binder composition, the properties of the bituminous binder composition such as penetrability, ball and ring temperature, viscosity, adhesiveness, complex modulus and properties. of bituminous mix obtained from said bituminous binder composition such as Duriez resistance, hiding resistance and modulus may be affected and become too far removed from the non-additive binder composition and the coated material obtained from said non-additive binder composition.
  • the alkylthiol additive of general formula (1) is essential to the process according to the invention and makes it possible to prepare mixes at lower manufacturing, processing and compacting temperatures and at very low levels in the composition.
  • bituminous binder This additive provides a very good adhesiveness and wettability of the bituminous binder composition vis-à-vis aggregates, the bituminous binder composition is very manageable, even at lower temperatures than those traditionally implemented.
  • the bituminous binder composition according to the invention may also comprise at least one polymer chosen from elastomers, plastomers and their mixtures.
  • thermoplastic elastomers such as random or block copolymers of styrene and butadiene, linear or star (SBR, SBS) or styrene and isoprene (SIS), copolymers which may be mentioned in an illustrative and nonlimiting manner, of ethylene and vinyl acetate, copolymers of ethylene and propene, ethylene / propene / diene terpolymers (EPDM), acrylonitrile / butadiene / styrene terpolymers (ABS), olefinic homopolymers and copolymers of ethylene ( or propylene, or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinylchlorides, rubber crumbs, butyl rubbers, polychloro
  • Preferred polymers are copolymers of styrene and butadiene.
  • the copolymer of styrene and butadiene advantageously has a content styrene weight ranging from 5% to 50% by weight, based on the total weight of copolymer, preferably from 20% to 40%>.
  • the styrene-butadiene copolymer advantageously has a weight content of butadiene, ranging from 50% to 95% by weight, relative to the total weight of the copolymer, preferably from 60% to 80% by weight.
  • the 1-4-double-butadiene units derived from butadiene and the 1-2-double-butadiene units derived from butadiene are distinguished.
  • units with double bonds 1-4 derived from butadiene is meant the units obtained via a 1,4-addition during the polymerization of butadiene.
  • 1,2-Butadiene double-bonded units are understood to mean the units obtained via a 1,2-addition during the polymerization of butadiene.
  • the result of this addition 1,2 is a so-called "pendant" vinyl double bond.
  • the styrene-butadiene copolymer has a content of 1,2-butadiene-derived double-chain units of between 5% and 80% by weight, based on the total weight of the butadiene units, preferably between 10%. and 50%>, more preferably between 15% and 40%.
  • the styrene-butadiene hydrocarbon copolymer has an average molecular weight Mw of between 4,000 and 500,000 daltons, preferably between 10,000 and 200,000, more preferably between 50,000 and 200,000, and even more preferably between 80,000 and 10,000. and 150,000.
  • the molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to the ASTM standard.
  • the styrene-butadiene copolymer may be linear or star-shaped, in the form of diblock, triblock and / or multi-branched.
  • the styrene-butadiene hydrocarbon copolymer may also optionally include a statistical hinge.
  • a mixture of copolymers of styrene and butadiene may be envisaged.
  • a quantity of polymer of 1 to 20% by weight relative to the total weight of the bituminous binder composition is used, preferably from 5 to 10%, more preferably from 2 to 4%.
  • This polymer may optionally be crosslinked.
  • the crosslinking agents that can be used are of a very varied nature and are chosen as a function of the type (s) of polymer (s) contained in the bituminous binder according to the invention.
  • the crosslinking agent may be selected from sulfur alone or in admixture with vulcanization accelerators.
  • vulcanization accelerators are either hydrocarbyl polysulfides, sulfur-donor vulcanization accelerators, or non-sulfur donor vulcanization accelerators.
  • the hydrocarbyl polysulfides can be chosen from those defined in the patent FR2528439.
  • the sulfur-donor vulcanization accelerators may be chosen from thiuram polysulfides, for example, tetrabutylthiuram disulfides, tetraethylthiuram disulfides and tetramethylthiuram disulfides.
  • the non-sulfur-donor vulcanization accelerators that may be used according to the invention may be sulfur-containing compounds chosen in particular from mercaptobenzothiazole and its derivatives, dithiocarbamates and its derivatives, and thiuram monosulfides and its derivatives.
  • zinc-2-mercaptobenzothiazole, zinc dibutyldithiocarbamate and tetramethylthiuram monosulphide may be mentioned.
  • the bituminous binder composition according to the invention may also comprise fluxing agents such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin.
  • the oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides, in esterified form, for example in the form of methyl ester.
  • bituminous binder composition according to the invention may also comprise waxes of animal, plant or hydrocarbon origin, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or Fischer-Trospch waxes. Polyethylene waxes or Fischer-Trospch waxes may optionally be oxidized. Amide waxes such as ethylene bis-stearamide may also be added.
  • bituminous binder composition according to the invention may also comprise resins of vegetable origin such as rosins.
  • bituminous binder composition according to the invention may also comprise acids such as polyphosphoric acid or diacids, in particular fatty diacids.
  • adhesion improvers and / or surfactants are chosen from alkyle-lamin derivatives, alkyl-polyamine derivatives, alkylamidopolyamine derivatives, alkyl amidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture.
  • the most widely used are tallow propylene diamines, tallow amido amines, quaternary ammoniums obtained by quaternization of tallow propylene diamines, and tallow propylene polyamines.
  • the amount of adhesiveness improving agents and / or agents surfactants in the bituminous binder additive composition according to the invention is between 0.1% and 2% by weight, preferably between 0.5% and 1% by weight.
  • bituminous binder composition comprises, by weight relative to the total mass of the bituminous binder composition:
  • bituminous binder composition comprises, by weight relative to the total mass of the bituminous binder composition:
  • bituminous binder composition comprises by weight relative to the total weight of the bituminous binder composition:
  • bituminous binder composition may also comprise other known additives, in particular from 0.1% to 2% of tackifier and / or surfactant or from 0.1% to 2% of agent for the capture of H 2 S known under the English name of "scavenger".
  • bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
  • bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
  • bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
  • alkylthiol additive of formula (1) 60 to 98.89% bitumen
  • the invention also relates to a process for preparing a bituminous binder composition, wherein the mixing temperature of the bitumen and the alkylthiol additive of general formula (1) is between 100 ° C and 190 ° C, preferably between 110 ° C and 180 ° C, more preferably between 120 ° C and 180 ° C.
  • the alkylthiol additive of general formula (1) is premixed with the polymer before addition in the bitumen.
  • a process for preparing a bituminous binder composition comprises the following steps:
  • the subject of the invention is also a method for preparing a bituminous mix, in which an additive bituminous binder composition according to the invention is mixed with aggregates.
  • the process for preparing the mixes is thus at lower temperatures than those conventionally used. This is known as a process for preparing "warm” and not “hot” bituminous mixes.
  • the process for preparing the mixes is characterized in that the mixture or coating of the aggregates with the additivated bituminous binder composition is carried out at a particularly low temperature, the coating or manufacturing temperature of the mix being between 100 ° C. C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the aggregates and the bituminous binder additive composition are either both at the same temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C, the additivated bituminous binder composition is at a temperature around 180 ° C and the aggregates are at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the temperature of the aggregates which dictates the overall coating temperature which will be between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the aggregates at the temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C and the bituminous binder composition additivée at the same temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the additive of the bituminous binder composition by the alkylthiol additive of the general formula (1) does not affect the viscosity of the bituminous binder composition and does not decrease it, when the viscosity of the composition of the bituminous binder is too important to allow the pumping of the bituminous binder composition, it is then preferred to use the additive bituminous binder composition at 180 ° C and the aggregates at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C C and 150 ° C, more preferably between 120 ° C and 140 ° C, the overall coating temperature is still between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the additivated bituminous binder composition is preferably at a temperature between 120 ° C and 190 ° C, preferably between 140 ° C and 180 ° C and the aggregates at a temperature between 100 ° C and 150 ° C ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C, the overall coating temperature being always between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the mixing time is the contact time between the bitumen and the aggregates necessary to obtain a complete coating of aggregates.
  • the mixing time is measured in the laboratory in a mixer.
  • the mixing time is an indicator of the ease of coating. The shorter the mixing time, the easier the coating.
  • the coating temperature is lower in the process according to the invention, the coating is of good quality and the coating time or so-called mixing time is not increased compared to a traditional process at higher temperature, it is even decreased.
  • the mixing time of the process according to the invention is between 2 seconds and 5 minutes, preferably between 2 seconds and 1 minute, more preferably between 10 seconds and 30 seconds. It is preferable that the mixing time is as short as possible to avoid the formation of fines and the change of distribution of the aggregates, which is one of the objectives of the present invention.
  • the mixture of the additive bituminous binder composition / aggregates is widespread.
  • the application temperature during the spreading of the mixture of the bituminous binder composition / aggregates is included between 80 ° C and 150 ° C, preferably between 90 ° C and 140 ° C, more preferably between 100 ° C and 140 ° C.
  • the whole is then compacted and the compacting temperature of the spilled mixture is between 70 ° C. and 140 ° C., preferably between 80 ° C. and 130 ° C., more preferably between 90 ° C. and 130 ° C.
  • the whole is then cooled to room temperature.
  • the invention also relates to bituminous mixes comprising a bituminous binder composition according to the invention, aggregates and optionally fillers.
  • the bituminous mix comprises from 1 to 10% by weight of the additive bituminous binder composition, relative to the total weight of the mix, preferably from 4 to 8% by weight.
  • the invention also relates to the use in a bitumen, of at least one alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer ranging from 18 to 110, to reduce temperatures of manufacture, implementation and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
  • this alkylthiol additive makes it possible to lower the coating temperatures of all the bitumens (hard grade bitumens, intermediate grade bitumens, soft grade bitumens), irrespective of their penetrability.
  • the additive is suitable for penetration bitumens of between 35 and 50 1/10 mm and penetration bitumens of between 10 and 20 1/10 mm.
  • This alkylthiol additive of general formula (1) in a bituminous binder composition as defined above makes it possible to lower said coating temperatures and to reduce the mixing time and / or to increase the workability of the bituminous mixes. while preserving the mechanical properties of said bituminous mixes, and this at very low levels of additives.
  • the use of the alkylthiol additive of general formula (1) makes it possible to obtain manufacturing or coating temperatures between 100 ° C. and 150 ° C., preferably between 110 ° C. C and 150 ° C, more preferably between 120 ° C and 140 ° C.
  • the use of the alkylthiol additive of general formula (1) makes it possible to obtain application temperatures during spraying between 80 ° C. and 150 ° C., preferably between 90 ° C. and 140 ° C., more preferably between 100 ° C and 140 ° C.
  • the use of the alkylthiol additive of general formula (1) makes it possible to obtain compacting temperatures between 70 ° C. and 140 ° C., preferably between 80 ° C.
  • alkylthiol additive of general formula (1) makes it possible to obtain mixing times between 2 seconds and 5 minutes, preferably between 5 seconds and 1 minute, more preferably between 10 seconds and 30 seconds.
  • the use of the alkylthiol additive of general formula (1) makes it possible to reduce the manufacturing temperatures of the mixes from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C. ° C, more preferably from 30 ° C to 50 ° C.
  • the use of the alkylthiol additive of general formula (1) makes it possible to reduce the temperatures of implementation during the spreading of the mixes from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C., more preferably from 30 ° C to 50 ° C.
  • the use of the alkylthiol additive of general formula (1) makes it possible to reduce the compaction temperatures from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C., more preferably from 30 ° C. to 50 ° C. vs.
  • the subject of the invention is the use of mixes according to the invention for the manufacture of road, pavement, sidewalk, road, urban development, soil, building waterproofing or road surfaces. works, in particular for the manufacture in road application, of foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
  • the subject of the invention is also a process for reducing the temperatures for the manufacture, implementation and / or compaction of an asphalt mix and / or for reducing the mixing time and / or increasing the workability of said bituminous mix, this process comprising at least one step in which is incorporated in a bituminous binder composition an alkylthiol of general formula (1) C n H2 n + i-SH.
  • the subject of the invention is also a process for reducing the temperatures for the manufacture, implementation and / or compaction of an asphalt mix and / or improving the mixing time and / or the workability of said mix, this method comprising at least one step in which an alkylthiol of the general formula (1) is introduced into a bituminous binder composition.
  • the subject of the invention is also a method for manufacturing road, pavement, sidewalk, road, urban development, floor, building or building waterproofing, in particular road-side manufacturing. , foundation layers, base layers, base layers, surface layers such as the tie layers and / or the wearing courses in which is implemented a mix as defined above.
  • the different products used are the following: - an AZALT ® 35/50 bitumen rated B ls having a penetrability of 40 1/10 mm (according to EN 1426) and a Ball and Ring Temperature of 52.2 ° C (according to the EN 1427) and commercially available from TOTAL,
  • alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer equal to 18 which is octadecyl mercaptan, denoted Ai, commercially available from the company ROBINSON BROTHERS LIMITED
  • bituminous binder compositions are prepared:
  • the bituminous binder composition Ci is a bituminous binder composition additive with the additive A1 described above.
  • the bituminous binder composition Ci comprises 79.2% by weight of bitumen Bi and 19.8% by weight of bitumen B 2 as defined above and 1% by weight of additive Ai.
  • the composition of bituminous binder C 2 is a bituminous binder composition additive with the additive A 2 described above.
  • the composition of bituminous binder C 2 comprises 99% by weight of bitumen Bi and 1% by weight of active ingredient of additive A 2 .
  • bituminous binder Cr is a bituminous binder composition additive with the additive Ai described above.
  • the Cr bituminous binder composition comprises 83.74% by weight of bitumen B ls 11, 42% by weight of bitumen B 2 , 3.5% by weight of polymer, 0.09% by weight of sulfur and 0.025%. > Nalco additive mass, as defined above and 1% by weight of additive Ai.
  • the bituminous binder composition C 2 ' is a bituminous binder composition additive with the additive A 2 described above.
  • Table 1 Compositions of bituminous binders
  • the penetrability is corrected to work with isopenetrability.
  • the adjustment of the penetrability for these compositions is achieved by adding the bitumen B 2 .
  • bituminous binder compositions C 1 , C 2 are prepared by mixing the compounds as defined above and the additive A 1 or A 2 respectively at a temperature of 180 ° C.
  • compositions of bituminous binder Cr, C 2 > are prepared by mixing the compounds as defined above and the additive A 1 or A 2 respectively at a temperature of approximately 180 ° C.
  • ⁇ R in Mpa is the compressive strength after 1 week in the air according to EN 12697-12
  • the various bituminous mixes E ls E 2 and Er, E 2 > are then prepared from 5.4% by weight respectively of the compositions of binders Ci, C 2 and Cr, C 2 > and granulates of the La Noubleau type containing 36 , 9% by mass of sand 0-2, 9.5% by mass of aggregates 2-4, 1 1, 4% by mass of aggregates 4-6, 36% by mass of aggregates 6-10 and 0 9% by weight of filler.
  • the asphalt mix according to the invention E 1 is prepared at the manufacturing temperature or coating temperature of 120 ° C., the aggregates being at a temperature of 120 ° C. and the composition of bituminous binder C 1 at 165 ° C. during seconds.
  • the bituminous mix according to the invention E 2 is prepared at the manufacturing temperature or coating temperature of 120 ° C, the aggregates being at a temperature of 120 ° C and the bituminous binder composition C 2 at 165 ° C , for 94 seconds.
  • the asphalt mix according to the invention Er is prepared at the manufacturing temperature or coating temperature of 140 ° C., the aggregates being at a temperature of 140 ° C. and the bituminous binder composition Cr at 175 ° C., while 77 seconds.
  • bituminous mix according to the invention E 2 - is prepared at the manufacturing temperature or coating temperature of 140 ° C, the aggregates being at a temperature of 120 ° C and the composition of bituminous binder C 2 'to 180 ° C, for 89 seconds.
  • the mixing time is reduced when the bituminous binder composition is additive with the additive according to the invention, as evidenced by the mixing times of the mixes E 1 and Er in comparison with the mixing times of the mixes E 2 respectively. and ⁇ 2 ⁇ obtained when the bituminous binder composition is additivated with another additive. It is therefore possible to prepare warm mixes at 120 ° C (Ei) or 140 ° C (Er) without increasing the mixing time and without degrading the properties of bituminous mixes. In particular, it can be seen that the compressive strength after storage in water or in air, obtained when the bituminous binder composition is additivated with the additive according to the invention, is of the same order of magnitude. aggregates at 120 ° C for C1 while a non-additive bitumen is conventionally used at 165 ° C according to conventional coating methods.
  • the coating temperature is lowered then the compaction temperature is also decreased.

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Abstract

The present invention relates to an additized bituminous binder composition comprising bitumen and at least one long-chain alkylthiol additive that permits a reduction in the manufacturing, utilization and compacting temperatures for the surfacing materials and in the mixing time, and an increase in the operational convenience of said surfacing materials. The invention also relates to methods for low-temperature production of the surfacing materials obtained from the additized bituminous binder composition. The invention relates, lastly, to the use of the additized bituminous binder composition for manufacturing more operationally convenient surfacing materials at lower temperatures and in lower mixing times, and to the use of these surfacing materials, in particular, in road application for foundation layers, base layers, lower layers and surface layers such as bonding layers and/or upper layers.

Description

COMPOSITION DE LIANT BITUMINEUX POUR LA PREPARATION D'ENROBES A BASSES TEMPERATURES  BITUMINOUS BINDER COMPOSITION FOR THE PREPARATION OF LOW TEMPERATURE COILS
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention concerne une composition de liant bitumineux additivée comprenant au moins un bitume et au moins un additif alkylthiol à longue chaîne permettant de diminuer les températures de fabrication, de mise en œuvre, de compactage des enrobés et de diminuer le temps de malaxage et/ou d'augmenter la maniabilité desdits enrobés. L'invention concerne aussi les enrobés obtenus à partir de ladite composition de liant bitumineux additivée avec l'alkylthiol à longue chaîne.  The present invention relates to an additivated bituminous binder composition comprising at least one bitumen and at least one long-chain alkylthiol additive making it possible to reduce the temperatures of manufacture, of implementation, of compaction of the mixes and to reduce the mixing time and / or or to increase the workability of said mixes. The invention also relates to the mixes obtained from said bituminous binder composition additive with long-chain alkylthiol.
L'invention concerne aussi les procédés de préparation à basses températures des enrobés obtenus à partir de ladite composition de liant bitumineux additivée avec l'alkylthiol à longue chaîne.  The invention also relates to processes for the preparation at low temperatures of the mixes obtained from said bituminous binder composition additivated with the long-chain alkylthiol.
L'invention concerne enfin l'utilisation de l'alkylthiol à longue chaîne dans une composition de liant bitumineux et l'utilisation de ladite composition de liant bitumineux additivée avec l'alkylthiol à longue chaîne, pour fabriquer à plus basses températures et à plus faible temps de malaxage des enrobés plus maniables.  The invention further relates to the use of the long chain alkylthiol in a bituminous binder composition and the use of said bituminous binder composition additive composition with the long chain alkylthiol, for manufacturing at lower temperatures and at lower temperatures. mixing time of the mixes more manageable.
L'invention concerne aussi l'utilisation de ces enrobés pour la fabrication de revêtements de routes, de chaussées, de trottoirs, de voiries, d'aménagements urbains, de sols, d'étanchéité de bâtiments ou d'ouvrages d'art, en particulier en applications routières pour la fabrication de couches de fondation, de couches de base, de couches d'assise, de couches de surface telles que les couches de liaison et/ou les couches de roulement.  The invention also relates to the use of these mixes for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, floors, waterproofing buildings or structures, in particularly in road applications for the manufacture of foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
ART ANTERIEUR PRIOR ART
Par enrobé bitumineux, on entend, un mélange d'une composition de liant bitumineux avec des granulats et éventuellement des charges minérales. Les granulats sont des granulats minéraux et/ou synthétiques, notamment, des fraisais de recyclage, de dimensions supérieures à 2 mm, de préférence comprises entre 2 mm et 20 mm et les charges minérales sont constituées de fines (particules de dimensions inférieures à 0,063 mm), de sable (particules de dimensions comprises entre 0,063 mm et 2 mm) et éventuellement de gravillons (particules de dimensions supérieures à 2 mm, de préférence comprises entre 2 mm et 4 mm). Selon l'invention, le terme granulat représente un granulat répondant aux exigences d'une utilisation routière. Ces granulats sont de préférence issus du concassage de roches massives ou de roches alluvionnaires. Les granulats désignent donc un matériau granulaire utilisé dans la construction. Un granulat peut être naturel, artificiel ou recyclé. Le terme "granulat naturel " désigne un granulat n'ayant subi aucune déformation autre que mécanique. Le terme " granulat artificiel " désigne un granulat d'origine minérale résultant d'un procédé industriel comprenant des transformations thermiques ou autres. Le terme " granulat recyclé " désigne un granulat obtenu par traitement d'une matière inorganique précédemment utilisée dans la construction. Les granulats utilisés sont des granulats routiers, répondant aux normes pertinentes : NF EN 13043 en Europe et ASTM C33 aux Etats-Unis d'Amérique. Les classes granulaires (d/D) des constituants de ces enrobés faisant l'objet de la série de normes produits français NF P98-130 à NF P98-141 pouvant être utilisés selon l'invention sont les suivantes : 0/2 (sable), 0/4, 2/4 (gravillons), 0/6,3, 2/6,3 et 4/6,3. Ces classes granulaires s'entendent au sens de la norme XP PI 8-540, remplacée aujourd'hui par la norme XP P18-545. By bituminous coating is meant a mixture of a bituminous binder composition with aggregates and optionally mineral fillers. The aggregates are inorganic and / or synthetic aggregates, in particular recycling mills with dimensions greater than 2 mm, preferably between 2 mm and 20 mm, and the mineral fillers consist of fines (particles smaller than 0.063 mm in size). ), sand (particles of dimensions between 0.063 mm and 2 mm) and possibly chippings (particles larger than 2 mm, preferably between 2 mm and 4 mm). According to the invention, the term granulate represents a granulate meeting the requirements of a road use. These aggregates are preferably derived from the crushing of massive rocks or alluvial rocks. Aggregates are therefore a granular material used in construction. A granulate can be natural, artificial or recycled. The term "natural granulate" designates a granulate having not undergone any deformation other than mechanical. The term "artificial granulate" refers to a granulate of mineral origin resulting from an industrial process including thermal or other transformations. The term "recycled granulate" refers to a granulate obtained by treatment of an inorganic material previously used in the construction. The aggregates used are road aggregates, meeting the relevant standards: NF EN 13043 in Europe and ASTM C33 in the United States of America. The granular classes (d / D) of the constituents of these mixes that are the subject of the series of French product standards NF P98-130 to NF P98-141 that can be used according to the invention are the following: 0/2 (sand) , 0/4, 2/4 (chippings), 0 / 6.3, 2 / 6.3 and 4 / 6.3. These granular classes are understood in the sense of the standard XP PI 8-540, replaced today by the standard XP P18-545.
Les enrobés sont utilisés pour fabriquer des routes et sont compactés au rouleau lors de leur mise en place.  Asphalt mixes are used to make roads and are compacted with rollers when they are put in place.
La préparation des enrobés à chaud comprend plusieurs étapes. La première étape consiste à mélanger la composition de liant bitumineux avec des granulats à une température dite de fabrication ou température d'enrobage. Le mélange composition de liant bitumineux/granulats ou le mélange composition de liant bitumineux/charges est ensuite répandu à une température dite de mise en œuvre. Il existe ensuite une étape de compactage à une température dite de compactage. Après le compactage de l'enrobé bitumineux, celui-ci est refroidi à température ambiante.  The preparation of hot mixes comprises several steps. The first step consists in mixing the bituminous binder composition with aggregates at a temperature called manufacturing temperature or coating temperature. The bituminous binder composition / aggregate mixture or the bituminous binder composition / filler mixture is then spread at a so-called processing temperature. There is then a compaction step at a so-called compacting temperature. After compaction of the bituminous mix, it is cooled to room temperature.
Les différentes températures mises en œuvre dans la préparation des enrobés sont très élevées. Ainsi, pour les enrobés bitumineux, les températures de fabrication (ou température d'enrobage) et de mise en œuvre sont comprises entre 160°C et 180°C, la température de compactage est comprise entre 120°C et 150°C.  The different temperatures used in the preparation of asphalt are very high. Thus, for bituminous mixes, the manufacturing temperature (or coating temperature) and implementation are between 160 ° C and 180 ° C, the compacting temperature is between 120 ° C and 150 ° C.
Ces températures relativement élevées, induisent de fortes dépenses énergétiques, des émissions de gaz à effet de serre et de composés organiques volatils.  These relatively high temperatures induce high energy costs, emissions of greenhouse gases and volatile organic compounds.
C'est pourquoi des techniques dites « à froid » ont été proposées. Ces techniques reposent sur l'utilisation d'émulsions de bitume, dispersions de bitume dans de l'eau. Les émulsions de bitume sont préparées à des températures inférieures à 100°C, mais nécessitent l'emploi d'eau et sont surtout utilisées pour la fabrication de chaussées faiblement à moyennement sollicitées car les performances mécaniques obtenues via ces techniques dites « à froid » sont en général en retrait lorsqu'elles sont comparées aux techniques dites « à chaud ».  This is why techniques called "cold" have been proposed. These techniques are based on the use of bitumen emulsions, dispersions of bitumen in water. The bitumen emulsions are prepared at temperatures below 100 ° C, but require the use of water and are mainly used for the manufacture of low to medium-stressed pavements because the mechanical performances obtained by these so-called "cold" techniques are generally indented when compared to so-called "hot" techniques.
Une autre voie pour abaisser les températures de préparation des enrobés à chaud, repose sur des techniques intermédiaires dites « tièdes », techniques qui ne font pas intervenir des émulsions de bitume. Elles font intervenir des additifs qui peuvent être anhydres ou présenter une certaine quantité d'eau. On cherche donc à abaisser les températures de fabrication, de mise en œuvre et de compactage des enrobés bitumineux tout en améliorant le temps de malaxage et/ou la maniabilité desdits enrobés. Diverses solutions pour abaisser lesdites températures, basées sur l'additivation de la composition de liant bitumineux ont déjà été proposées. Another way to lower the preparation temperature of hot mixes, based on so-called "warm" intermediate techniques, which do not involve bitumen emulsions. They involve additives that can be anhydrous or have a certain amount of water. It is therefore sought to lower the temperatures of manufacture, implementation and compaction of bituminous mix while improving the mixing time and / or maneuverability of said asphalt. Various solutions for lowering said temperatures, based on the additivation of the bituminous binder composition have already been proposed.
La demande de brevet WO2007135097 décrit l'utilisation d'une combinaison de deux additifs dans une composition de liant pour réduire la température de fabrication et/ou de mise en œuvre d'un produit bitumineux. Le premier additif est un composé macro moléculaire choisi parmi les résines naturelles d'origine végétale ou les cires d'hydrocarbures. Le deuxième additif est un dérivé d'acides gras choisi dans le groupe constitué par les diesters d'acides gras et les éthers d'acides gras.  The patent application WO2007135097 describes the use of a combination of two additives in a binder composition to reduce the temperature of manufacture and / or implementation of a bituminous product. The first additive is a macro-molecular compound chosen from natural resins of vegetable origin or hydrocarbon waxes. The second additive is a fatty acid derivative selected from the group consisting of fatty acid diesters and fatty acid ethers.
La demande WO200906295 décrit l'utilisation d'une combinaison d'additifs pour préparer des enrobés tièdes. La combinaison d'additifs comprend un agent surfactant et modificateur de rhéologie comprenant une cire et une résine.  The application WO200906295 describes the use of a combination of additives for preparing warm mixes. The additive combination comprises a surfactant and rheology modifier comprising a wax and a resin.
La demande de brevet EP2192158 décrit l'utilisation d'au moins un triglycéride d'acides gras dans une composition de liant bitumineux pour réduire la température de fabrication d'enrobés à chaud.  Patent application EP2192158 describes the use of at least one fatty acid triglyceride in a bituminous binder composition to reduce the hot mix production temperature.
La demande de brevet EP2062941 décrit l'utilisation d'au moins 10% en poids de glycérol dans une composition de liant bitumineux pour réduire la température de fabrication des enrobés à chaud.  The patent application EP2062941 describes the use of at least 10% by weight of glycerol in a bituminous binder composition to reduce the temperature of manufacture of hot mixes.
Dans le brevet JP4334730, à l'aide d'une technique à froid, une émulsion de bitume est employée, la composition de liant bitumineux étant additivée par un produit de réaction entre une polyalkylène-polyamine et un anhydride alkénylsucinique et par une résine de polyoléfme portant des groupes carboxyles et ayant un indice d'acide compris entre 5 et 100 mg KOH/g. Ce mélange permet de préparer des émulsions de bitume améliorées.  In patent JP4334730, using a cold technique, a bitumen emulsion is used, the bituminous binder composition being additivated by a reaction product between a polyalkylene polyamine and an alkenylsucin anhydride and a polyolefin resin. carrying carboxyl groups and having an acid number of between 5 and 100 mg KOH / g. This mixture makes it possible to prepare improved bitumen emulsions.
La demande de brevet FR2965271 décrit l'utilisation d'un additif de type anhydride succinique ou succinimide dans une composition de liant bitumineux pour diminuer la température de fabrication, de mise en œuvre et/ou de compactage d'enrobés tièdes.  The patent application FR2965271 describes the use of a succinic anhydride or succinimide additive in a bituminous binder composition to reduce the temperature of manufacture, implementation and / or compaction of warm mixes.
RESUME DE L'INVENTION  SUMMARY OF THE INVENTION
Dans cette perspective, la société demanderesse a cherché à trouver un additif alternatif aux additifs existants, permettant de diminuer les températures de fabrication, de mise en œuvre et de compactage des enrobés tout en améliorant les temps de malaxage et/ou la maniabilité desdits enrobés.  In this perspective, the applicant company has sought to find an alternative additive to existing additives, to reduce the manufacturing temperature, implementation and compaction of the mix while improving the mixing times and / or the workability of said mixes.
Selon l'invention, cet additif est un alkylthiol de formule générale (1) CnH2n+i-SH, qui présente l'avantage de pouvoir être utilisé seul et pas en mélange ou en combinaison avec d'autres additifs, comme c'est le cas dans l'art antérieur. L'objectif principal de la présente invention est donc de proposer un procédé de préparation d'enrobés à plus basses températures, afin de réduire la consommation énergétique, de réduire le rejet des gaz de combustion et de réduire les émissions de fumées. According to the invention, this additive is an alkylthiol of general formula (1) C n H 2n + i-SH, which has the advantage that it can be used alone and not in admixture or combination with other additives, such as c is the case in the prior art. The main objective of the present invention is therefore to provide a process for preparing asphalt at lower temperatures, in order to reduce energy consumption, reduce the discharge of flue gases and reduce smoke emissions.
Un autre objectif de la présente invention est de proposer un procédé de préparation d'enrobés à plus basses températures, qui soit économique, car mettant en œuvre une faible teneur en additif.  Another object of the present invention is to provide a process for preparing asphalt at lower temperatures, which is economical because implementing a low additive content.
Un autre objectif de la présente invention est de proposer un procédé de préparation d'enrobés à plus basses températures, dans lequel les propriétés de la composition de liant additivée ne sont pas ou peu modifiées par rapport au bitume de base non additivé. Ainsi les propriétés telles que la consistance (pénétrabilité, température Bille et Anneau) ou la viscosité de la composition de liant additivée ne doivent pas être modifiées.  Another object of the present invention is to provide a process for the preparation of asphalt at lower temperatures, in which the properties of the additive binder composition are not changed or little modified compared to the non-additive base bitumen. Thus properties such as consistency (penetrability, Ball and Ring temperature) or viscosity of the additive binder composition should not be changed.
Un autre objectif de la présente invention est de proposer un procédé de préparation d'enrobés à plus basses températures, permettant d'assurer une bonne adhésivité de la composition de liant bitumineux additivée/granulats et permettant un faible désenrobage.  Another object of the present invention is to provide a process for the preparation of asphalt at lower temperatures, to ensure good adhesiveness of the bituminous binder composition additive / aggregates and allowing a low stripping.
Un autre objectif de la présente invention est de proposer un procédé de préparation d'enrobés à plus basses températures qui soit anhydre.  Another object of the present invention is to provide a method for preparing asphalt at lower temperatures which is anhydrous.
Un autre objectif de la présente invention est de proposer un procédé de préparation d'enrobés à plus basses températures, les enrobés obtenus par ledit procédé ayant des propriétés mécaniques équivalentes ou améliorées par rapport aux enrobés traditionnels, classiquement fabriqués à partir des procédés connus à plus hautes températures.  Another object of the present invention is to provide a process for the preparation of mixes at lower temperatures, the mixes obtained by said process having equivalent or improved mechanical properties compared to conventional mixes, conventionally manufactured from known processes at higher temperatures. high temperatures.
En particulier, un des objectifs de la présente invention est de proposer un enrobé tiède fabriqué à plus basses températures, ayant une bonne résistance au désenrobage.  In particular, one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to stripping.
En particulier, un des objectifs de la présente invention est de proposer un enrobé tiède fabriqué à plus basses températures, ayant une bonne résistance à l'orniérage.  In particular, one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to rutting.
En particulier, un des objectifs de la présente invention est de proposer un enrobé tiède fabriqué à plus basses températures, ayant un bon module de rigidité.  In particular, one of the objectives of the present invention is to provide a warm mix manufactured at lower temperatures, having a good modulus of rigidity.
L'invention concerne une composition de liant bitumineux comprenant au moins un bitume et au moins un additif alkylthiol de formule générale (1) CnH2n+i- SH dans laquelle n représente un entier variant de 18 à 110. The invention relates to a bituminous binder composition comprising at least one bitumen and at least one alkylthiol additive of general formula (1) C n H2 n + 1-SH wherein n represents an integer ranging from 18 to 110.
L'invention concerne aussi une composition de liant bitumineux comprenant de 0,1 à 20% en masse d'additif alkylthiol de formule (1), par rapport à la masse totale de la composition de liant bitumineux. L' invention concerne aussi une composition de liant bitumineux comprenant en outre un polymère choisi parmi les élastomères, les plastomères et leurs mélanges. The invention also relates to a bituminous binder composition comprising from 0.1 to 20% by weight of alkylthiol additive of formula (1), based on the total weight of the bituminous binder composition. The invention also relates to a bituminous binder composition further comprising a polymer selected from elastomers, plastomers and mixtures thereof.
L'invention concerne aussi une composition de liant bitumineux comprenant en outre un agent réticulant.  The invention also relates to a bituminous binder composition further comprising a crosslinking agent.
L'invention concerne aussi un procédé de préparation d'une composition de liant bitumineux telle que décrite ci-dessus comprenant le mélange de l'additif alkylthiol de formule générale (1) et du bitume à une température comprise entre 100°C et 190°C.  The invention also relates to a process for preparing a bituminous binder composition as described above comprising mixing the alkylthiol additive of general formula (1) and bitumen at a temperature of between 100 ° C. and 190 ° C. vs.
L'invention concerne aussi un procédé de préparation d'une composition de liant bitumineux telle que décrite ci-dessus comprenant en outre un polymère choisi parmi les élastomères, les plastomères et leurs mélanges, ledit procédé comprenant les étapes suivantes :  The invention also relates to a process for preparing a bituminous binder composition as described above further comprising a polymer chosen from elastomers, plastomers and mixtures thereof, said process comprising the following steps:
- mélange du polymère et de l'additif alkylthiol de formule générale (1), mixture of the polymer and the alkylthiol additive of general formula (1),
- ajout dudit mélange dans le bitume à une température comprise entre 100°C et 190°C. adding said mixture to the bitumen at a temperature of between 100 ° C. and 190 ° C.
L'invention concerne aussi un enrobé bitumineux comprenant une composition de liant bitumineux et des granulats comprenant éventuellement des fines, du sable, des gravillons.  The invention also relates to a bituminous mix comprising a bituminous binder composition and aggregates optionally comprising fines, sand, chippings.
L'invention concerne aussi un procédé de préparation d'un enrobé bitumineux comprenant le mélange de la composition de liant bitumineux telle que définie ci-dessus avec des granulats, dans lequel la température d'enrobage est comprise entre 100°C et 150°C.  The invention also relates to a process for the preparation of a bituminous mix comprising mixing the bituminous binder composition as defined above with aggregates, in which the coating temperature is between 100 ° C. and 150 ° C. .
L'invention concerne aussi un procédé de préparation d'un enrobé bitumineux dans lequel la composition de liant bitumineux et les granulats sont tous deux à une température comprise entre 100°C et 150°C.  The invention also relates to a process for preparing a bituminous mix in which the bituminous binder composition and the aggregates are both at a temperature of between 100 ° C and 150 ° C.
L'invention concerne aussi un procédé de préparation d'un enrobé bitumineux dans lequel la température de mise en œuvre lors du répandage du mélange composition de liant bitumineux/granulats est comprise entre 80°C et 150°C.  The invention also relates to a process for the preparation of a bituminous mix in which the application temperature during spreading of the bituminous binder / aggregate composition mixture is between 80 ° C. and 150 ° C.
L'invention concerne aussi un procédé de préparation d'un enrobé bitumineux dans lequel la température de compactage du mélange répandu est comprise entre 70°C et 140°C.  The invention also relates to a process for preparing a bituminous mix in which the compacting temperature of the spilled mixture is between 70 ° C. and 140 ° C.
L'invention concerne aussi un procédé de préparation d'un enrobé bitumineux dans lequel le temps de malaxage est compris entre 2 secondes et 5 minutes.  The invention also relates to a process for preparing a bituminous mix in which the mixing time is between 2 seconds and 5 minutes.
L'invention concerne aussi l'utilisation d'un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier variant de 18 à 110, dans une composition de liant bitumineux pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou diminuer le temps de malaxage et/ou augmenter la maniabilité dudit enrobé. The invention also relates to the use of an alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer varying from 18 to 110, in a bituminous binder composition to reduce the temperature manufacture, implementation and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
L'invention concerne aussi l'utilisation d'une composition de liant bitumineux telle que définie ci-dessus pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou améliorer le temps de malaxage et/ou la maniabilité dudit enrobé.  The invention also relates to the use of a bituminous binder composition as defined above for reducing the temperatures of manufacture, implementation and / or compaction of a bituminous mix and / or improving the mixing time. and / or the workability of said mix.
L'invention concerne aussi l'utilisation d'un enrobé pour la fabrication de revêtements de routes, de chaussées, de trottoirs, de voiries, d'aménagements urbains, de sols, d'étanchéité de bâtiments ou d'ouvrages, en particulier pour la fabrication en application routière, de couches de fondation, de couches de base, de couches d'assise, de couches de surface telles que les couches de liaison et/ou les couches de roulement.  The invention also relates to the use of an asphalt mix for the manufacture of road, pavement, sidewalk, road, urban development, floor, building or building waterproofing, particularly for the manufacture in road application, foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
DESCRIPTION DETAILLEE DETAILED DESCRIPTION
Composition de liant bitumineux  Bituminous binder composition
La composition de liant bitumineux comprend au moins un bitume et au moins un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier variant de 18 à 110. The bituminous binder composition comprises at least one bitumen and at least one alkylthiol additive of the general formula (1) C n H 2n + i-SH wherein n represents an integer ranging from 18 to 110.
L'additif alkylthiol comprend une chaîne hydrocarbonée saturée, linéaire ou ramifiée, d'au moins 18 atomes de carbone. De préférence la chaîne hydrocarbonée saturée de l'alkylthiol est linéaire. La chaîne hydrocarbonée saturée de l'alkylthiol a pour formule générale CnH2n+1, où n représente un entier supérieur ou égal à 18, de préférence variant de 18 à 110, de préférence variant de 18 à 90, de préférence variant de 18 à 50, de préférence variant de 18 à 40 et de préférence variant de 18 à 30. Le C30H61 SH est par exemple commercialisé par Connect Marketing Gmbh. The alkylthiol additive comprises a saturated hydrocarbon chain, linear or branched, of at least 18 carbon atoms. Preferably, the saturated hydrocarbon chain of the alkylthiol is linear. The saturated hydrocarbon chain of alkylthiol has the general formula C n H 2n + 1 , where n represents an integer greater than or equal to 18, preferably ranging from 18 to 110, preferably ranging from 18 to 90, preferably ranging from 18 to 50, preferably ranging from 18 to 40 and preferably ranging from 18 to 30. C30H61 SH is for example marketed by Connect Marketing GmbH.
La composition de liant bitumineux comprend au moins un bitume. Ce bitume est pris seul ou en mélange. Parmi les bitumes utilisables selon l'invention, on peut citer tout d'abord les bitumes d'origine naturelle, ceux contenus dans des gisements de bitume naturel, d'asphalte naturel ou les sables bitumineux. Les bitumes selon l'invention comprennent aussi les bitumes provenant du raffinage du pétrole brut. Les bitumes proviennent de la distillation atmosphérique et/ou sous vide du pétrole. Ces bitumes pouvant être éventuellement soufflés, viscoréduits et/ou désasphaltés. Les différents bitumes obtenus par les procédés de raffinage peuvent être combinés entre eux pour obtenir le meilleur compromis technique. Le bitume peut aussi être un bitume de recyclage. Les bitumes peuvent être des bitumes de grade dur ou de grade mou. Les bitumes selon l'invention ont une pénétrabilité, mesurée à 25°C selon la norme EN 1426, comprise entre 5 et 200 1/10 mm, de préférence entre 10 et 100 1/10 mm, plus préférentiellement entre 20 et 60 1/10 mm, encore plus préférentiellement entre 30 et 50 1/10 mm. The bituminous binder composition comprises at least one bitumen. This bitumen is taken alone or mixed. Among the bitumens that can be used according to the invention, mention may be made first of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands. Bitumens according to the invention also include bitumens derived from the refining of crude oil. Bitumens come from the atmospheric and / or vacuum distillation of oil. These bitumens can be optionally blown, vis-reduced and / or deasphalted. The different bitumens obtained by the refining processes can be combined with one another to obtain the best technical compromise. Bitumen can also be a recycling bitumen. The bitumens may be hard grade or soft grade bitumens. The bitumens according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, of between 5 and 200 1/10 mm, of preferably between 10 and 100 1/10 mm, more preferably between 20 and 60 1/10 mm, even more preferably between 30 and 50 1/10 mm.
La composition de liant bitumineux additivée selon l'invention comprend de 0,1 à 20% en masse d'additif alkylthiol de formule générale (1), par rapport à la masse totale de la composition de liant bitumineux, de préférence de 0,5 à 10%> en masse, plus préférentiellement de 0,7 à 5% en masse, encore plus préférentiellement de 0,8 à 2%> en masse.  The additive bituminous binder composition according to the invention comprises from 0.1 to 20% by weight of alkylthiol additive of general formula (1), relative to the total mass of the bituminous binder composition, preferably from 0.5 at 10% by weight, more preferably from 0.7 to 5% by weight, more preferably from 0.8 to 2% by weight.
On préfère utiliser une quantité d'additif la plus faible possible, pour des raisons économiques, mais aussi techniques. En effet si l'additif est présent en quantité importante dans la composition de liant bitumineux, les propriétés de la composition de liant bitumineux telles que la pénétrabilité, la température Bille et Anneau, la viscosité, l'adhésivité, le module complexe et les propriétés de l'enrobé bitumineux obtenu à partir de ladite composition de liant bitumineux telles que la résistance Duriez, la résistance à l'omiérage et le module, peuvent en être affectées et devenir trop éloignées de celles de la composition de liant non additivée et de l'enrobé obtenu à partir de ladite composition de liant non additivée.  It is preferred to use the smallest amount of additive possible, for economic reasons, but also technical. Indeed, if the additive is present in a significant amount in the bituminous binder composition, the properties of the bituminous binder composition such as penetrability, ball and ring temperature, viscosity, adhesiveness, complex modulus and properties. of bituminous mix obtained from said bituminous binder composition such as Duriez resistance, hiding resistance and modulus may be affected and become too far removed from the non-additive binder composition and the coated material obtained from said non-additive binder composition.
L'additif alkylthiol de formule générale (1) est essentiel au procédé selon l'invention et permet de préparer des enrobés à des températures de fabrication, de mise en œuvre, et de compactage plus basses et ce à de très faibles teneurs dans la composition de liant bitumineux. Cet additif permet une très bonne adhésivité et mouillabilité de la composition de liant bitumineux vis-à-vis des granulats, la composition de liant bitumineux est très maniable et ce même à des températures plus basses que celles mises en œuvre traditionnellement.  The alkylthiol additive of general formula (1) is essential to the process according to the invention and makes it possible to prepare mixes at lower manufacturing, processing and compacting temperatures and at very low levels in the composition. bituminous binder. This additive provides a very good adhesiveness and wettability of the bituminous binder composition vis-à-vis aggregates, the bituminous binder composition is very manageable, even at lower temperatures than those traditionally implemented.
La composition de liant bitumineux selon l'invention, peut également comprendre au moins un polymère choisi parmi les élastomères, les plastomères et leurs mélanges. On peut citer par exemple, de manière indicative et non limitative, les élastomères thermoplastiques comme les copolymères statistiques ou séquencés de styrène et de butadiène, linéaire ou en étoile (SBR, SBS) ou de styrène et d'isoprène (SIS), les copolymères d'éthylène et d'acétate de vinyle, les copolymères d'éthylène et de propène, les terpolymères éthylène/propène/diène (EPDM), les terpolymères acrylonitrile/butadiène/styrène (ABS), les homopolymères et copolymères oléfmiques d'éthylène (ou propylène, ou butylène), les polyisobutylènes, les polybutadiènes, les polyisoprènes, les poly(chlorure de vinyle), les poudrettes de caoutchouc, les caoutchoucs butyle, les polychloroprènes, les polynorbornènes, les polybutènes, les polyisobutènes, les polyéthylènes ou encore tout polymère utilisé pour la modification des bitumes ainsi que leurs mélanges.  The bituminous binder composition according to the invention may also comprise at least one polymer chosen from elastomers, plastomers and their mixtures. For example, thermoplastic elastomers such as random or block copolymers of styrene and butadiene, linear or star (SBR, SBS) or styrene and isoprene (SIS), copolymers which may be mentioned in an illustrative and nonlimiting manner, of ethylene and vinyl acetate, copolymers of ethylene and propene, ethylene / propene / diene terpolymers (EPDM), acrylonitrile / butadiene / styrene terpolymers (ABS), olefinic homopolymers and copolymers of ethylene ( or propylene, or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinylchlorides, rubber crumbs, butyl rubbers, polychloroprenes, polynorbornenes, polybutenes, polyisobutenes, polyethylenes or else polymer used for the modification of bitumens as well as their mixtures.
Les polymères préférés sont les copolymères de styrène et de butadiène. Le copolymère de styrène et de butadiène, possède avantageusement une teneur pondérale en styrène allant de 5% à 50% en masse, par rapport à la masse totale de copolymère, de préférence de 20% à 40%>. Preferred polymers are copolymers of styrene and butadiene. The copolymer of styrene and butadiene advantageously has a content styrene weight ranging from 5% to 50% by weight, based on the total weight of copolymer, preferably from 20% to 40%>.
Le copolymère de styrène et de butadiène possède avantageusement une teneur pondérale en butadiène, allant de 50% à 95% en masse, par rapport à la masse totale de copolymère, de préférence de 60%> à 80%>.  The styrene-butadiene copolymer advantageously has a weight content of butadiene, ranging from 50% to 95% by weight, relative to the total weight of the copolymer, preferably from 60% to 80% by weight.
Parmi les motifs butadiène, on distingue les motifs à doubles liaisons 1-4 issus du butadiène et les motifs à doubles liaisons 1-2 issus du butadiène. Par motifs à doubles liaisons 1-4 issus du butadiène, on entend les motifs obtenus via une addition 1,4 lors de la polymérisation du butadiène. Par motifs à doubles liaisons 1-2 issus du butadiène, on entend les motifs obtenus via une addition 1,2 lors de la polymérisation du butadiène. Le résultat de cette addition 1,2 est une double liaison vinylique dite « pendante ».  Among the butadiene units, the 1-4-double-butadiene units derived from butadiene and the 1-2-double-butadiene units derived from butadiene are distinguished. By units with double bonds 1-4 derived from butadiene is meant the units obtained via a 1,4-addition during the polymerization of butadiene. 1,2-Butadiene double-bonded units are understood to mean the units obtained via a 1,2-addition during the polymerization of butadiene. The result of this addition 1,2 is a so-called "pendant" vinyl double bond.
Le copolymère de styrène et de butadiène possède une teneur en motifs à doubles liaisons 1-2 issus du butadiène, comprise entre 5%> et 80%> en masse, par rapport à la masse totale des motifs butadiène, de préférence entre 10%> et 50%>, plus préférentiellement entre 15% et 40%.  The styrene-butadiene copolymer has a content of 1,2-butadiene-derived double-chain units of between 5% and 80% by weight, based on the total weight of the butadiene units, preferably between 10%. and 50%>, more preferably between 15% and 40%.
Le copolymère d'hydrocarbure de styrène et de butadiène, a une masse moléculaire moyenne Mw comprise entre 4 000 et 500 000 daltons, de préférence entre 10 000 et 200 000, plus préférentiellement entre 50 000 et 200 000, encore plus préférentiellement entre 80 000 et 150 000. La masse moléculaire du copolymère est mesurée par chromatographie GPC avec un étalon polystyrène selon la norme ASTM The styrene-butadiene hydrocarbon copolymer has an average molecular weight Mw of between 4,000 and 500,000 daltons, preferably between 10,000 and 200,000, more preferably between 50,000 and 200,000, and even more preferably between 80,000 and 10,000. and 150,000. The molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to the ASTM standard.
D3536 (remplacée par la norme ASTM D5296-05). D3536 (superseded by ASTM D5296-05).
Le copolymère de styrène et de butadiène peut être linéaire ou étoilé, sous forme de dibloc, de tribloc et/ou être multibranché. Le copolymère d'hydrocarbure de styrène et de butadiène peut aussi comprendre éventuellement une charnière statistique. Un mélange de copolymères de styrène et de butadiène peut être envisagé.  The styrene-butadiene copolymer may be linear or star-shaped, in the form of diblock, triblock and / or multi-branched. The styrene-butadiene hydrocarbon copolymer may also optionally include a statistical hinge. A mixture of copolymers of styrene and butadiene may be envisaged.
On utilise en général une quantité de polymère de 1 à 20% en masse par rapport à la masse totale de la composition de liant bitumineux, de préférence de 5 à 10%), plus préférentiellement de 2 à 4%>.  In general, a quantity of polymer of 1 to 20% by weight relative to the total weight of the bituminous binder composition is used, preferably from 5 to 10%, more preferably from 2 to 4%.
Ce polymère peut éventuellement être réticulé. Les agents réticulants utilisables sont de nature très variée et sont choisis en fonction du ou des type(s) de polymère(s) contenu(s) dans le liant bitumineux selon l'invention. L'agent réticulant peut être choisi parmi le soufre seul ou en mélange avec des accélérateurs de vulcanisation. Ces accélérateurs de vulcanisation sont soit des polysulfures d'hydrocarbyle, soit des accélérateurs de vulcanisation donneurs de soufre, soit des accélérateurs de vulcanisation non donneurs de soufre. Les polysulfures d'hydrocarbyle peuvent être choisis parmi ceux qui sont définis dans le brevet FR2528439. Les accélérateurs de vulcanisation donneurs de soufre, peuvent être choisis parmi les polysulfures de thiurame, comme par exemple, les disulfures de tétrabutylthiurame, les disulfures de tétraéthylthiurame et les disulfures de tétraméthylthiurame. Les accélérateurs de vulcanisation non donneurs de soufre utilisables selon l'invention peuvent être des composés soufrés choisis notamment parmi le mercaptobenzothiazole et ses dérivés, les dithiocarbamates et ses dérivés, et les monosulfures de thiurame et ses dérivés. On peut citer par exemple le zinc-2- mercaptobenzothiazole, le dibutyldithiocarbamate de zinc, le monosulfure de tétraméthylthiurame. Pour plus de détails sur les accélérateurs de vulcanisation donneurs de soufre et non donneurs de soufre utilisables selon l'invention, on peut se référer aux brevets EP0360656, EP0409683 et FR2528439. On utilise en général une quantité d'agent réticulant de 0,01 à 2% en masse par rapport à la masse totale de la composition de liant bitumineux, de préférence de 0,05 à 1%. This polymer may optionally be crosslinked. The crosslinking agents that can be used are of a very varied nature and are chosen as a function of the type (s) of polymer (s) contained in the bituminous binder according to the invention. The crosslinking agent may be selected from sulfur alone or in admixture with vulcanization accelerators. These vulcanization accelerators are either hydrocarbyl polysulfides, sulfur-donor vulcanization accelerators, or non-sulfur donor vulcanization accelerators. The hydrocarbyl polysulfides can be chosen from those defined in the patent FR2528439. The sulfur-donor vulcanization accelerators may be chosen from thiuram polysulfides, for example, tetrabutylthiuram disulfides, tetraethylthiuram disulfides and tetramethylthiuram disulfides. The non-sulfur-donor vulcanization accelerators that may be used according to the invention may be sulfur-containing compounds chosen in particular from mercaptobenzothiazole and its derivatives, dithiocarbamates and its derivatives, and thiuram monosulfides and its derivatives. For example, zinc-2-mercaptobenzothiazole, zinc dibutyldithiocarbamate and tetramethylthiuram monosulphide may be mentioned. For more details on the sulfur-donor and non-sulfur-donor vulcanization accelerators that can be used according to the invention, reference can be made to patents EP0360656, EP0409683 and FR2528439. In general, an amount of crosslinking agent of 0.01 to 2% by weight is used, based on the total weight of the bituminous binder composition, preferably 0.05 to 1%.
La composition de liant bitumineux selon l'invention peut également comprendre des fluxants tels que des huiles à base de matières grasses animales et/ou végétales ou des huiles hydrocarbonées d'origine pétrolière. Les huiles d'origine animale et/ou végétale pourront être sous forme d'acides gras libres, de triglycérides, de diglycérides, de monoglycérides, sous forme estérifïée, par exemple sous forme d'ester méthylique.  The bituminous binder composition according to the invention may also comprise fluxing agents such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin. The oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides, in esterified form, for example in the form of methyl ester.
La composition de liant bitumineux selon l'invention peut aussi comprendre des cires d'origine animale, végétale ou d'hydrocarbures, en particulier des cires hydrocarbonées à chaîne longue, par exemple des cires de polyéthylène ou des cires Fischer-Trospch. Les cires de polyéthylène ou les cires Fischer-Trospch pourront éventuellement être oxydées. Les cires amides telles que l'éthylène bis-stéaramide pourront aussi être ajoutées.  The bituminous binder composition according to the invention may also comprise waxes of animal, plant or hydrocarbon origin, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or Fischer-Trospch waxes. Polyethylene waxes or Fischer-Trospch waxes may optionally be oxidized. Amide waxes such as ethylene bis-stearamide may also be added.
La composition de liant bitumineux selon l'invention peut aussi comprendre des résines d'origine végétale telles que les colophanes.  The bituminous binder composition according to the invention may also comprise resins of vegetable origin such as rosins.
La composition de liant bitumineux selon l'invention peut aussi comprendre des acides tels que l'acide polyphosphorique ou des diacides, en particuliers des diacides gras.  The bituminous binder composition according to the invention may also comprise acids such as polyphosphoric acid or diacids, in particular fatty diacids.
On peut également ajouter à la composition de liant bitumineux additivée selon l'invention, des agents améliorant l'adhésivité et/ou des agents tensioactifs. Ils sont choisis parmi les dérivés d'alky lamines, les dérivés d'alkyl-polyamines, les dérivés d'alkylamidopolyamines, les dérivés d'alkyl amidopolyamines et les dérivés de sels d'ammonium quaternaire, pris seuls ou en mélange. Les plus utilisés sont les propylènes-diamines de suif, les amido-amines de suif, les ammoniums quaternaires obtenus par quaternisation des propylènes-diamines de suif, les propylènes- polyamines de suif. La quantité d'agents améliorant l'adhésivité et/ou des agents tensioactifs dans la composition de liant bitumineux additivée selon l'invention est comprise entre 0,1% et 2% en masse, de préférence entre 0,5% et 1% en masse. To the additive bituminous binder composition according to the invention, it is also possible to add adhesion improvers and / or surfactants. They are chosen from alkyle-lamin derivatives, alkyl-polyamine derivatives, alkylamidopolyamine derivatives, alkyl amidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture. The most widely used are tallow propylene diamines, tallow amido amines, quaternary ammoniums obtained by quaternization of tallow propylene diamines, and tallow propylene polyamines. The amount of adhesiveness improving agents and / or agents surfactants in the bituminous binder additive composition according to the invention is between 0.1% and 2% by weight, preferably between 0.5% and 1% by weight.
On pourrait aussi ajouter des dérivés du sorbitol, des dérivés hydrazides, des dérivés de type imidazolidinone.  It is also possible to add sorbitol derivatives, hydrazide derivatives and imidazolidinone derivatives.
Selon un mode de réalisation particulier, la composition de liant bitumineux comprend en masse par rapport à la masse totale de la composition de liant bitumineux :  According to one particular embodiment, the bituminous binder composition comprises, by weight relative to the total mass of the bituminous binder composition:
- 0,1 à 20% d'additif alkylthiol de formule (1)  0.1 to 20% of alkylthiol additive of formula (1)
- 80 à 99,9 % de bitume  - 80 to 99.9% bitumen
Avantageusement, la composition de liant bitumineux comprend en masse par rapport à la masse totale de la composition de liant bitumineux :  Advantageously, the bituminous binder composition comprises, by weight relative to the total mass of the bituminous binder composition:
- 0,1 à 20% d'additif alkylthiol de formule (1)  0.1 to 20% of alkylthiol additive of formula (1)
- 60 à 98,9 % de bitume  - 60 to 98.9% bitumen
1 à 20%) de polymère  1 to 20%) of polymer
De préférence, la composition de liant bitumineux comprend en masse par rapport à la masse totale de la composition de liant bitumineux :  Preferably, the bituminous binder composition comprises by weight relative to the total weight of the bituminous binder composition:
- 0,1 à 20% d'additif alkylthiol de formule (1)  0.1 to 20% of alkylthiol additive of formula (1)
- 60 à 98,89 % de bitume  - 60 to 98.89% bitumen
1 à 20%) de polymère  1 to 20%) of polymer
0,01 à 2% d'agent réticulant  0.01 to 2% crosslinking agent
En outre, la composition de liant bitumineux peut également comprendre d'autres additifs connus, en particulier de 0,1 % à 2% d'agent améliorant l'adhésivité et/ou d'agent tensio-actif ou de 0,1% à 2% d'agent pour la captation de H2S connus sous le nom anglais de « scavenger ». In addition, the bituminous binder composition may also comprise other known additives, in particular from 0.1% to 2% of tackifier and / or surfactant or from 0.1% to 2% of agent for the capture of H 2 S known under the English name of "scavenger".
Selon un autre mode de réalisation particulier, la composition de liant bitumineux consiste essentiellement en masse par rapport à la masse totale de la composition de liant bitumineux :  According to another particular embodiment, the bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
- 0,1 à 20% d'additif alkylthiol de formule (1)  0.1 to 20% of alkylthiol additive of formula (1)
- 80 à 99,9 % de bitume  - 80 to 99.9% bitumen
Avantageusement, la composition de liant bitumineux consiste essentiellement en masse par rapport à la masse totale de la composition de liant bitumineux :  Advantageously, the bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
- 0,1 à 20% d'additif alkylthiol de formule (1)  0.1 to 20% of alkylthiol additive of formula (1)
- 60 à 98,9 % de bitume  - 60 to 98.9% bitumen
1 à 20%) de polymère  1 to 20%) of polymer
De préférence, la composition de liant bitumineux consiste essentiellement en masse par rapport à la masse totale de la composition de liant bitumineux :  Preferably, the bituminous binder composition consists essentially of mass relative to the total mass of the bituminous binder composition:
- 0, 1 à 20% d'additif alkylthiol de formule (1) - 60 à 98,89 % de bitume 0.1 to 20% of alkylthiol additive of formula (1) - 60 to 98.89% bitumen
1 à 20% de polymère  1 to 20% of polymer
0,01 à 2% d'agent réticulant  0.01 to 2% crosslinking agent
Procédés de préparation d'une composition de liant bitumineux et d'un enrobé bitumineux  Processes for preparing a bituminous binder and bituminous mix composition
L'invention a aussi pour objet un procédé de préparation d'une composition de liant bitumineux, dans lequel la température de mélange du bitume et de l'additif alkylthiol de formule générale (1) est comprise entre 100°C et 190°C, de préférence entre 110°C et 180°C, plus préférentiellement entre 120°C et 180°C.  The invention also relates to a process for preparing a bituminous binder composition, wherein the mixing temperature of the bitumen and the alkylthiol additive of general formula (1) is between 100 ° C and 190 ° C, preferably between 110 ° C and 180 ° C, more preferably between 120 ° C and 180 ° C.
Selon un autre mode de réalisation particulier, l'additif alkylthiol de formule générale (1) est mélangé préalablement avec le polymère avant addition dans le bitume. En particulier, un procédé de préparation d'une composition de liant bitumineux comprend les étapes suivantes :  According to another particular embodiment, the alkylthiol additive of general formula (1) is premixed with the polymer before addition in the bitumen. In particular, a process for preparing a bituminous binder composition comprises the following steps:
- mélange du polymère et de l'additif alkylthiol de formule générale (1),  mixture of the polymer and the alkylthiol additive of general formula (1),
- ajout dudit mélange dans le bitume à une température comprise entre 100°C et 190°C. adding said mixture to the bitumen at a temperature of between 100 ° C. and 190 ° C.
L'invention a également pour objet un procédé de préparation d'un enrobé bitumineux, dans lequel on mélange une composition de liant bitumineux additivée selon l'invention avec des granulats.  The subject of the invention is also a method for preparing a bituminous mix, in which an additive bituminous binder composition according to the invention is mixed with aggregates.
Grâce à l'utilisation de l'additif alkylthiol de formule générale (1) CnH2n+i-By using the alkylthiol additive of general formula (1) C n H2 n + i-
SH tel que décrit ci-dessus dans une composition de liant bitumineux, le procédé de préparation des enrobés se fait ainsi à des températures plus basses que celles classiquement utilisées. On parle ainsi de procédé de préparation d'enrobés bitumineux dits « tièdes » et non plus « chauds ». SH as described above in a bituminous binder composition, the process for preparing the mixes is thus at lower temperatures than those conventionally used. This is known as a process for preparing "warm" and not "hot" bituminous mixes.
Le procédé de préparation des enrobés est caractérisé par le fait que le mélange ou enrobage des granulats avec la composition de liant bitumineux additivée se fait à une température particulièrement basse, la température d'enrobage ou de fabrication de l'enrobé étant comprise entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C.  The process for preparing the mixes is characterized in that the mixture or coating of the aggregates with the additivated bituminous binder composition is carried out at a particularly low temperature, the coating or manufacturing temperature of the mix being between 100 ° C. C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
Lors de l'enrobage, les granulats et la composition de liant bitumineux additivée sont soit tous les deux à la même température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C, soit la composition de liant bitumineux additivée est à une température autour de 180°C et les granulats sont à une température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C. En raison de la quantité importante de granulats par rapport à la composition de liant bitumineux additivée (à peu près 95% en masse de granulats par rapport à 5% en masse de composition de liant bitumineux additivée), c'est la température des granulats qui dicte la température globale d'enrobage qui sera donc entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C. On préfère utiliser les granulats à la température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C et la composition de liant bitumineux additivée à la même température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C. During coating, the aggregates and the bituminous binder additive composition are either both at the same temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C, the additivated bituminous binder composition is at a temperature around 180 ° C and the aggregates are at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C. Due to the large quantity of aggregates with respect to the additivated bituminous binder composition (approximately 95% by weight of aggregates with respect to 5% by weight of additive bituminous binder composition), it is the temperature of the aggregates which dictates the overall coating temperature which will be between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C. It is preferred to use the aggregates at the temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C and the bituminous binder composition additivée at the same temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
Etant donné que l'additivation de la composition de liant bitumineux par l'additif alkylthiol de formule générale (1) ne joue pas sur la viscosité de la composition de liant bitumineux et ne diminue pas celle-ci, lorsque la viscosité de la composition de liant bitumineux est trop importante pour permettre le pompage de la composition de liant bitumineux, on préfère alors utiliser la composition de liant bitumineux additivée vers 180°C et les granulats à une température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C, la température globale d'enrobage étant alors quand même comprise entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C. Dans ce cas-là, la composition de liant bitumineux additivée est de préférence à une température comprise entre 120°C et 190°C, de préférence entre 140°C et 180°C et les granulats à une température entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C, la température globale d'enrobage étant toujours comprise entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C.  Since the additive of the bituminous binder composition by the alkylthiol additive of the general formula (1) does not affect the viscosity of the bituminous binder composition and does not decrease it, when the viscosity of the composition of the bituminous binder is too important to allow the pumping of the bituminous binder composition, it is then preferred to use the additive bituminous binder composition at 180 ° C and the aggregates at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C C and 150 ° C, more preferably between 120 ° C and 140 ° C, the overall coating temperature is still between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C. In this case, the additivated bituminous binder composition is preferably at a temperature between 120 ° C and 190 ° C, preferably between 140 ° C and 180 ° C and the aggregates at a temperature between 100 ° C and 150 ° C ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C, the overall coating temperature being always between 100 ° C and 150 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 140 ° C.
Le temps de malaxage est le temps de contact entre le bitume et les granulats nécessaire pour obtenir un enrobage des granulats complet. Le temps de malaxage est mesuré en laboratoire dans un malaxeur. Le temps de malaxage est un indicateur de la facilité d'enrobage. Plus le temps de malaxage est court, plus l'enrobage est facile.  The mixing time is the contact time between the bitumen and the aggregates necessary to obtain a complete coating of aggregates. The mixing time is measured in the laboratory in a mixer. The mixing time is an indicator of the ease of coating. The shorter the mixing time, the easier the coating.
Bien que la température d'enrobage soit plus faible dans le procédé selon l'invention, l'enrobage est de bonne qualité et le temps d'enrobage ou temps dit de malaxage n'est pas augmenté par rapport à un procédé traditionnel à plus haute température, celui-ci est même diminué. Ainsi le temps de malaxage du procédé selon l'invention est compris entre 2 secondes et 5 minutes, de préférence entre 2 secondes et 1 minute, plus préférentiellement entre 10 secondes et 30 secondes. Il est préférable que le temps de malaxage soit le plus court possible pour éviter la formation de fines et le changement de distribution des granulats, ce qui est l'un des objectifs de la présente invention.  Although the coating temperature is lower in the process according to the invention, the coating is of good quality and the coating time or so-called mixing time is not increased compared to a traditional process at higher temperature, it is even decreased. Thus the mixing time of the process according to the invention is between 2 seconds and 5 minutes, preferably between 2 seconds and 1 minute, more preferably between 10 seconds and 30 seconds. It is preferable that the mixing time is as short as possible to avoid the formation of fines and the change of distribution of the aggregates, which is one of the objectives of the present invention.
Une fois les granulats enrobés, le mélange de la composition de liant bitumineux additivée/granulats est répandu. La température de mise en œuvre lors du répandage du mélange de la composition de liant bitumineux/granulats est comprise entre 80°C et 150°C, de préférence entre 90°C et 140°C, plus préférentiellement entre 100°C et 140°C. Le tout est ensuite compacté et la température de compactage du mélange répandu est comprise entre 70°C et 140°C, de préférence entre 80°C et 130°C, plus préférentiellement entre 90°C et 130°C. L'ensemble est ensuite refroidi à température ambiante. Once the aggregates are coated, the mixture of the additive bituminous binder composition / aggregates is widespread. The application temperature during the spreading of the mixture of the bituminous binder composition / aggregates is included between 80 ° C and 150 ° C, preferably between 90 ° C and 140 ° C, more preferably between 100 ° C and 140 ° C. The whole is then compacted and the compacting temperature of the spilled mixture is between 70 ° C. and 140 ° C., preferably between 80 ° C. and 130 ° C., more preferably between 90 ° C. and 130 ° C. The whole is then cooled to room temperature.
Enrobés bitumineux  Asphalt mix
L'invention a également pour objet des enrobés bitumineux comprenant une composition de liant bitumineux selon l'invention, des granulats et éventuellement des charges. L'enrobé bitumineux comprend de 1 à 10 % en masse de la composition de liant bitumineux additivée, par rapport à la masse totale de l'enrobé, de préférence de 4 à 8% en masse.  The invention also relates to bituminous mixes comprising a bituminous binder composition according to the invention, aggregates and optionally fillers. The bituminous mix comprises from 1 to 10% by weight of the additive bituminous binder composition, relative to the total weight of the mix, preferably from 4 to 8% by weight.
Utilisations de l'additif alkylthiol  Uses of the alkylthiol additive
L'invention a aussi pour objet l'utilisation dans un bitume, d'au moins un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier variant de 18 à 110, pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou diminuer le temps de malaxage et/ou augmenter la maniabilité dudit enrobé. The invention also relates to the use in a bitumen, of at least one alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer ranging from 18 to 110, to reduce temperatures of manufacture, implementation and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
L'utilisation de cet additif alkylthiol permet d'abaisser lesdites températures d'enrobage de tous les bitumes (bitumes de grade dur, bitumes de grade intermédiaire, bitumes de grade mou), quelque soit leur pénétrabilité. Ainsi l'additif est adapté aux bitumes de pénétrabilité comprise entre 35 et 50 1/10 mm et aux bitumes de pénétrabilité comprise entre 10 et 20 1/10 mm.  The use of this alkylthiol additive makes it possible to lower the coating temperatures of all the bitumens (hard grade bitumens, intermediate grade bitumens, soft grade bitumens), irrespective of their penetrability. Thus the additive is suitable for penetration bitumens of between 35 and 50 1/10 mm and penetration bitumens of between 10 and 20 1/10 mm.
Cet additif alkylthiol de formule générale (1) dans une composition de liant bitumineux telle que définie ci-dessus, permet d'abaisser lesdites températures d'enrobage ainsi que de diminuer le temps de malaxage et/ou d'augmenter la maniabilité des enrobés bitumineux, tout en préservant les propriétés mécaniques desdits enrobés bitumineux, et ce à de très faibles teneurs en additifs.  This alkylthiol additive of general formula (1) in a bituminous binder composition as defined above makes it possible to lower said coating temperatures and to reduce the mixing time and / or to increase the workability of the bituminous mixes. while preserving the mechanical properties of said bituminous mixes, and this at very low levels of additives.
L'utilisation de l'additif alkylthiol de formule générale (1), lors de la fabrication d'un enrobé, permet d'obtenir des températures de fabrication ou d'enrobage entre 100°C et 150°C, de préférence entre 110°C et 150°C, plus préférentiellement entre 120°C et 140°C. L'utilisation de l'additif alkylthiol de formule générale (1), permet d'obtenir des températures de mise en œuvre lors du répandage entre 80°C et 150°C, de préférence entre 90°C et 140°C, plus préférentiellement entre 100°C et 140°C. L'utilisation de l'additif alkylthiol de formule générale (1), permet d'obtenir des températures de compactage entre 70°C et 140°C, de préférence entre 80°C et 130°C, plus préférentiellement entre 90°C et 130°C. L'utilisation de l'additif alkylthiol de formule générale (1), permet d'obtenir des temps de malaxage entre 2 secondes et 5 minutes, de préférence entre 5 secondes et 1 minute, plus préférentiellement entre 10 secondes et 30 secondes. The use of the alkylthiol additive of general formula (1), during the manufacture of an asphalt mix, makes it possible to obtain manufacturing or coating temperatures between 100 ° C. and 150 ° C., preferably between 110 ° C. C and 150 ° C, more preferably between 120 ° C and 140 ° C. The use of the alkylthiol additive of general formula (1) makes it possible to obtain application temperatures during spraying between 80 ° C. and 150 ° C., preferably between 90 ° C. and 140 ° C., more preferably between 100 ° C and 140 ° C. The use of the alkylthiol additive of general formula (1) makes it possible to obtain compacting temperatures between 70 ° C. and 140 ° C., preferably between 80 ° C. and 130 ° C., more preferably between 90 ° C. and 130 ° C. The use of the alkylthiol additive of general formula (1) makes it possible to obtain mixing times between 2 seconds and 5 minutes, preferably between 5 seconds and 1 minute, more preferably between 10 seconds and 30 seconds.
L'utilisation de l'additif alkylthiol de formule générale (1), lors de la fabrication d'un enrobé, permet de diminuer les températures de fabrication des enrobés de 10°C à 80°C, de préférence de 20°C à 60°C, plus préférentiellement de 30°C à 50°C. L'utilisation de l'additif alkylthiol de formule générale (1) permet de diminuer les températures de mise en œuvre lors du répandage des enrobés de 10°C à 80°C, de préférence de 20°C à 60°C, plus préférentiellement de 30°C à 50°C. L'utilisation de l'additif alkylthiol de formule générale (1) permet de diminuer les températures de compactage de 10°C à 80°C, de préférence de 20°C à 60°C, plus préférentiellement de 30°C à 50°C.  The use of the alkylthiol additive of general formula (1), during the manufacture of an asphalt mix, makes it possible to reduce the manufacturing temperatures of the mixes from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C. ° C, more preferably from 30 ° C to 50 ° C. The use of the alkylthiol additive of general formula (1) makes it possible to reduce the temperatures of implementation during the spreading of the mixes from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C., more preferably from 30 ° C to 50 ° C. The use of the alkylthiol additive of general formula (1) makes it possible to reduce the compaction temperatures from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C., more preferably from 30 ° C. to 50 ° C. vs.
L'invention a enfin pour objet, l'utilisation d'enrobés selon l'invention pour la fabrication de revêtements de routes, de chaussées, de trottoirs, de voiries, d'aménagements urbains, de sols, d'étanchéité de bâtiments ou d'ouvrages, en particulier pour la fabrication en application routière, de couches de fondation, de couches de base, de couches d'assise, de couches de surface telles que les couches de liaison et/ou les couches de roulement. L'invention a encore pour objet un procédé pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou diminuer le temps de malaxage et/ou augmenter la maniabilité dudit enrobé, ce procédé comprenant au moins une étape au cours de laquelle on incorpore dans une composition de liant bitumineux un alkylthiol de formule générale (1) CnH2n+i-SH. Finally, the subject of the invention is the use of mixes according to the invention for the manufacture of road, pavement, sidewalk, road, urban development, soil, building waterproofing or road surfaces. works, in particular for the manufacture in road application, of foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses. The subject of the invention is also a process for reducing the temperatures for the manufacture, implementation and / or compaction of an asphalt mix and / or for reducing the mixing time and / or increasing the workability of said bituminous mix, this process comprising at least one step in which is incorporated in a bituminous binder composition an alkylthiol of general formula (1) C n H2 n + i-SH.
L'invention a encore pour objet un procédé pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou améliorer le temps de malaxage et/ou la maniabilité dudit enrobé, ce procédé comprenant au moins une étape au cours de laquelle on introduit un alkylthiol de formule générale (1) dans une composition de liant bitumineux. The subject of the invention is also a process for reducing the temperatures for the manufacture, implementation and / or compaction of an asphalt mix and / or improving the mixing time and / or the workability of said mix, this method comprising at least one step in which an alkylthiol of the general formula (1) is introduced into a bituminous binder composition.
L'invention a encore pour objet un procédé de fabrication de revêtements de routes, de chaussées, de trottoirs, de voiries, d'aménagements urbains, de sols, d'étanchéité de bâtiments ou d'ouvrages, en particulier de fabrication en application routière, de couches de fondation, de couches de base, de couches d'assise, de couches de surface telles que les couches de liaison et/ou les couches de roulement dans lequel est mis en œuvre un enrobé tel que défini ci-dessus. EXEMPLES The subject of the invention is also a method for manufacturing road, pavement, sidewalk, road, urban development, floor, building or building waterproofing, in particular road-side manufacturing. , foundation layers, base layers, base layers, surface layers such as the tie layers and / or the wearing courses in which is implemented a mix as defined above. EXAMPLES
Les différents produits utilisés sont les suivants : - un bitume AZALT® 35/50 noté Bl s ayant une pénétrabilité de 40 1/10 mm (selon la norme EN 1426) et une Température Bille et Anneau de 52,2°C (selon la norme EN 1427) et disponible commercialement auprès de la société TOTAL, The different products used are the following: - an AZALT ® 35/50 bitumen rated B ls having a penetrability of 40 1/10 mm (according to EN 1426) and a Ball and Ring Temperature of 52.2 ° C (according to the EN 1427) and commercially available from TOTAL,
- un bitume MODULOTAL® 10/20 noté B2, ayant une pénétrabilité de 13 1/10 mm (selon la norme EN 1426) disponible commercialement auprès de la société TOTAL, - un polymère KRATON® D1 192 disponible commercialement auprès de la société KRATON a MODULOTAL ® 10/20 bitumen rated B 2 , having a penetrability of 13 1/10 mm (according to the EN 1426 standard) commercially available from TOTAL, - a KRATON ® D1 192 polymer commercially available from the company KRATON
- un soufre fourni par la société POLYTECHS  a sulfur supplied by the company POLYTECHS
- un additif Scavenger Nalco® EC5020A fourni par la société NALCO - Scavenger Nalco ® EC5020A additive supplied by NALCO
- un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier égal à 18 qui est l'octadecyl mercaptan, noté Ai, disponible commercialement auprès de la société ROBINSON BROTHERS LIMITED - an alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer equal to 18 which is octadecyl mercaptan, denoted Ai, commercially available from the company ROBINSON BROTHERS LIMITED
- un additif polyisobutylène succinimide noté A2, disponible commercialement auprès de la société Lubrizol. Différentes compositions de liant bitumineux sont préparées : a polyisobutylene succinimide additive noted A 2 , commercially available from Lubrizol. Various bituminous binder compositions are prepared:
- La composition de liant bitumineux Ci est une composition de liant bitumineux additivée avec l'additif Ai décrit ci-dessus. La composition de liant bitumineux Ci comprend 79,2% en masse de bitume Bi et 19,8% en masse de bitume B2 tels que définis ci-dessus et 1% en masse d'additif Ai . - The bituminous binder composition Ci is a bituminous binder composition additive with the additive A1 described above. The bituminous binder composition Ci comprises 79.2% by weight of bitumen Bi and 19.8% by weight of bitumen B 2 as defined above and 1% by weight of additive Ai.
- La composition de liant bitumineux C2 est une composition de liant bitumineux additivée avec l'additif A2 décrit ci-dessus. La composition de liant bitumineux C2 comprend 99% en masse de bitume Bi et 1% en masse de matière active d'additif A2.- The composition of bituminous binder C 2 is a bituminous binder composition additive with the additive A 2 described above. The composition of bituminous binder C 2 comprises 99% by weight of bitumen Bi and 1% by weight of active ingredient of additive A 2 .
- La composition de liant bitumineux Cr est une composition de liant bitumineux additivée avec l'additif Ai décrit ci-dessus. La composition de liant bitumineux Cr comprend 83,74%> en masse de bitume Bl s 1 1 ,42% en masse de bitume B2, 3,5% en masse de polymère, 0,09% en masse de soufre et 0,025%> en masse d'additif Nalco, tels que défini ci-dessus et 1% en masse d'additif Ai . - The composition of bituminous binder Cr is a bituminous binder composition additive with the additive Ai described above. The Cr bituminous binder composition comprises 83.74% by weight of bitumen B ls 11, 42% by weight of bitumen B 2 , 3.5% by weight of polymer, 0.09% by weight of sulfur and 0.025%. > Nalco additive mass, as defined above and 1% by weight of additive Ai.
- La composition de liant bitumineux C2' est une composition de liant bitumineux additivée avec l'additif A2 décrit ci-dessus. La composition de liant bitumineux C2' comprend 84,73%> en masse de bitume Bl s 10,43% en masse de bitume B2, 3,5% en masse de polymère, 0,09% en masse de soufre et 0,025%> en masse d'additif Nalco, tels que défini ci-dessus et 1% en masse de matière active d'additif A2. Tableau 1 : Compositions des liants bitumineux - The bituminous binder composition C 2 'is a bituminous binder composition additive with the additive A 2 described above. The bituminous binder composition C 2 'comprises 84.73% by weight of bitumen B ls 10.43% by mass of bitumen B 2 , 3.5% by weight of polymer, 0.09% by mass of sulfur and 0.025 %> by weight of Nalco additive, as defined above and 1% by weight of active ingredient of additive A 2 . Table 1: Compositions of bituminous binders
Pour les compositions Ci, Cr et C2, la pénétrabilité est corrigée pour travailler à isopénétrabilité. L'ajustement de la pénétrabilité pour ces compositions est réalisé par ajout du bitume B2. For the compositions Ci, Cr and C 2 , the penetrability is corrected to work with isopenetrability. The adjustment of the penetrability for these compositions is achieved by adding the bitumen B 2 .
On prépare les compositions de liant bitumineux Ci, C2 en mélangeant les composés tels que définis ci-dessus et respectivement l'additif Ai ou A2 à une température de 180°C. The bituminous binder compositions C 1 , C 2 are prepared by mixing the compounds as defined above and the additive A 1 or A 2 respectively at a temperature of 180 ° C.
On prépare les compositions de liant bitumineux Cr, C2> en mélangeant les composés tels que définis ci-dessus et respectivement l'additif Ai ou A2 à une température d'environ 180°C. The compositions of bituminous binder Cr, C 2 > are prepared by mixing the compounds as defined above and the additive A 1 or A 2 respectively at a temperature of approximately 180 ° C.
On constate que la présence d'alkylthiol Ai en tant qu'additif dans une composition de liant bitumineux ne modifie pas les propriétés de ladite composition d'après les valeurs de Température Bille et Anneau obtenues (voir valeurs de TBA dans le tableau 2 ci-dessous). Tableau 2 : Propriétés des compositions des liants bitumineux et des enrobés bitumineux It is found that the presence of alkylthiol Ai as an additive in a bituminous binder composition does not modify the properties of said composition from the obtained Ball and Ring Temperature values (see TBA values in Table 2 below). below). Table 2: Properties of the compositions of bituminous binders and bituminous mixes
Pénétrabilité en 1/10 mm mesurée selon la norme EN 1426  Penetration in 1/10 mm measured according to EN 1426
^Température Bille et Anneau mesurée selon la norme EN 1427  ^ Ball and ring temperature measured according to EN 1427
^Essai de résistance au désenrobage à l'eau selon la norme NF P 98-251-1 , reflète l'adhésion entre le liant bitumineux et les granulats  ^ Water stripping resistance test according to standard NF P 98-251-1, reflects the adhesion between the bituminous binder and the aggregates
en Mpa est la résistance à la compression après 1 semaine dans l'eau selon la norme EN 12697-12  in Mpa is the compressive strength after 1 week in water according to EN 12697-12
^R en Mpa est la résistance à la compression après 1 semaine dans l'air selon la norme EN 12697-12  ^ R in Mpa is the compressive strength after 1 week in the air according to EN 12697-12
On prépare ensuite les différents enrobés bitumineux El s E2 et Er, E2> à partir de 5,4% en masse respectivement des compositions de liants Ci, C2 et Cr, C2> et de granulats de type La Noubleau contenant 36,9% en masse de sable 0-2, 9,5%> en masse de granulats 2-4, 1 1 ,4%> en masse de granulats 4-6, 36%> en masse de granulats 6-10 et 0,9%> en masse de fïller. The various bituminous mixes E ls E 2 and Er, E 2 > are then prepared from 5.4% by weight respectively of the compositions of binders Ci, C 2 and Cr, C 2 > and granulates of the La Noubleau type containing 36 , 9% by mass of sand 0-2, 9.5% by mass of aggregates 2-4, 1 1, 4% by mass of aggregates 4-6, 36% by mass of aggregates 6-10 and 0 9% by weight of filler.
- L'enrobé bitumineux selon l'invention Ei est préparé à la température de fabrication ou température d'enrobage de 120°C, les granulats étant à une température de 120°C et la composition de liant bitumineux Ci àl65°C, pendant 81 secondes.  The asphalt mix according to the invention E 1 is prepared at the manufacturing temperature or coating temperature of 120 ° C., the aggregates being at a temperature of 120 ° C. and the composition of bituminous binder C 1 at 165 ° C. during seconds.
- L'enrobé bitumineux selon l'invention E2 est préparé à la température de fabrication ou température d'enrobage de 120°C, les granulats étant à une température de 120°C et la composition de liant bitumineux C2 à 165°C, pendant 94 secondes. - L'enrobé bitumineux selon l'invention Er est préparé à la température de fabrication ou température d'enrobage de 140°C, les granulats étant à une température de 140°C et la composition de liant bitumineux Cr à 175°C, pendant 77 secondes. - The bituminous mix according to the invention E 2 is prepared at the manufacturing temperature or coating temperature of 120 ° C, the aggregates being at a temperature of 120 ° C and the bituminous binder composition C 2 at 165 ° C , for 94 seconds. The asphalt mix according to the invention Er is prepared at the manufacturing temperature or coating temperature of 140 ° C., the aggregates being at a temperature of 140 ° C. and the bituminous binder composition Cr at 175 ° C., while 77 seconds.
- L'enrobé bitumineux selon l'invention E2- est préparé à la température de fabrication ou température d'enrobage de 140°C, les granulats étant à une température de 120°C et la composition de liant bitumineux C2' à 180°C, pendant 89 secondes. - The bituminous mix according to the invention E 2 - is prepared at the manufacturing temperature or coating temperature of 140 ° C, the aggregates being at a temperature of 120 ° C and the composition of bituminous binder C 2 'to 180 ° C, for 89 seconds.
On constate que le temps de malaxage est diminué lorsque la composition de liant bitumineux est additivée avec l'additif selon l'invention, comme en témoignent les temps de malaxage des enrobés Ei et Er en comparaison respectivement avec les temps de malaxages des enrobés E2 et Ε2· obtenus lorsque la composition de liant bitumineux est additivée avec un autre additif. Il est donc possible de préparer des enrobés tièdes à 120°C (Ei) ou 140°C (Er) sans augmenter le temps de malaxage et sans dégrader les propriétés des enrobés bitumineux. Notamment, on constate que la résistance à la compression après stockage dans l'eau ou dans l'air, obtenue lorsque la composition de liant bitumineux est additivée avec l'additif selon l'invention est du même ordre de grandeur On réussit l'enrobage des granulats à 120°C pour Ci alors qu'un bitume non additivé est classiquement utilisé à 165°C selon les procédés d'enrobage conventionnels. It can be seen that the mixing time is reduced when the bituminous binder composition is additive with the additive according to the invention, as evidenced by the mixing times of the mixes E 1 and Er in comparison with the mixing times of the mixes E 2 respectively. and Ε 2 · obtained when the bituminous binder composition is additivated with another additive. It is therefore possible to prepare warm mixes at 120 ° C (Ei) or 140 ° C (Er) without increasing the mixing time and without degrading the properties of bituminous mixes. In particular, it can be seen that the compressive strength after storage in water or in air, obtained when the bituminous binder composition is additivated with the additive according to the invention, is of the same order of magnitude. aggregates at 120 ° C for C1 while a non-additive bitumen is conventionally used at 165 ° C according to conventional coating methods.
De même, on réussit l'enrobage des granulats à 140°C pour Cr alors qu'un bitume/polymère non additivé est classiquement utilisé à 175°C selon les procédés d'enrobage conventionnels. L'ajout dans un bitume de l'additif alkylthiol selon la présente invention permet donc de diminuer la température d'enrobage. In the same way, it is possible to coat the aggregates at 140 ° C. for Cr while a non-additive bitumen / polymer is conventionally used at 175 ° C. according to the conventional coating methods. The addition in a bitumen of the alkylthiol additive according to the present invention thus makes it possible to reduce the coating temperature.
Si la température d'enrobage est abaissée alors la température de compactage est également diminuée. If the coating temperature is lowered then the compaction temperature is also decreased.

Claims

REVENDICATIONS
1. Composition de liant bitumineux comprenant au moins un bitume et au moins un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier variant de 18 à 110. 1. Bituminous binder composition comprising at least one bitumen and at least one alkylthiol additive of general formula (1) C n H 2n + i-SH wherein n represents an integer of 18-110.
2. Composition de liant bitumineux selon la revendication 1 comprenant de 0,1 à 20% en masse d'additif alkylthiol de formule (1), par rapport à la masse totale de la composition de liant bitumineux.  A bituminous binder composition according to claim 1 comprising from 0.1 to 20% by weight of alkylthiol additive of formula (1), based on the total weight of the bituminous binder composition.
3. Composition de liant bitumineux selon l'une quelconque des revendications 1 à 2 comprenant en outre un polymère choisi parmi les élastomères, les plastomères et leurs mélanges.  3. bituminous binder composition according to any one of claims 1 to 2 further comprising a polymer selected from elastomers, plastomers and mixtures thereof.
4. Composition de liant bitumineux selon l'une quelconque des revendications 1 à 3 comprenant en outre un agent réticulant.  4. A bituminous binder composition according to any one of claims 1 to 3 further comprising a crosslinking agent.
5. Procédé de préparation d'une composition de liant bitumineux selon l'une quelconque des revendications 1 à 4, comprenant le mélange de l'additif alkylthiol de formule générale (1) et du bitume à une température comprise entre 100°C et 190°C. Process for the preparation of a bituminous binder composition according to any one of claims 1 to 4, comprising mixing the alkylthiol additive of the general formula (1) and the bitumen at a temperature of between 100 ° C. and 190 ° C. ° C.
6. Procédé selon la revendication 5 dans lequel la composition de liant bitumineux comprend en outre un polymère choisi parmi les élastomères, les plastomères et leurs mélanges, ledit procédé comprenant les étapes suivantes : The method of claim 5 wherein the bituminous binder composition further comprises a polymer selected from elastomers, plastomers, and mixtures thereof, said process comprising the steps of:
- mélange du polymère et de l'additif alkylthiol de formule générale (1), mixture of the polymer and the alkylthiol additive of general formula (1),
- ajout dudit mélange dans le bitume à une température comprise entre 100°C et 190°C.  adding said mixture to the bitumen at a temperature of between 100 ° C. and 190 ° C.
7. Enrobé bitumineux comprenant une composition de liant bitumineux selon l'une quelconque des revendications 1 à 4 et des granulats comprenant éventuellement des fines, du sable, des gravillons.  7. Bituminous mix comprising a bituminous binder composition according to any one of claims 1 to 4 and aggregates optionally comprising fines, sand, chippings.
8. Procédé de préparation d'un enrobé bitumineux selon la revendication 7, comprenant le mélange de la composition de liant bitumineux telle que définie dans les revendications 1 à 4 avec des granulats, dans lequel la température d'enrobage est comprise entre 100°C et 150°C.  The process for the preparation of a bituminous mix according to claim 7, comprising mixing the bituminous binder composition as defined in claims 1 to 4 with aggregates, wherein the coating temperature is between 100 ° C. and 150 ° C.
9. Procédé de préparation d'un enrobé bitumineux selon la revendication 8, dans lequel la composition de liant bitumineux et les granulats sont tous deux à une température comprise entre 100°C et 150°C. The process for preparing a bituminous mix according to claim 8, wherein the bituminous binder composition and the aggregates are both at a temperature of 100 ° C to 150 ° C.
10. Procédé de préparation d'un enrobé bitumineux selon la revendication 8 ou 9, dans lequel la température de mise en œuvre lors du répandage du mélange composition de liant bitumineux/granulats est comprise entre 80°C et 150°C.  The process for preparing an asphalt mix according to claim 8 or 9, wherein the application temperature during spreading of the asphalt binder / aggregate composition mixture is from 80 ° C to 150 ° C.
11. Procédé de préparation d'un enrobé bitumineux selon l'une quelconque des revendications 8 à 10, dans lequel la température de compactage du mélange répandu est comprise entre 70°C et 140°C. 11. A process for preparing an asphalt mix according to any one of claims 8 to 10, wherein the compaction temperature of the spilled mixture is between 70 ° C and 140 ° C.
12. Procédé de préparation d'un enrobé bitumineux selon l'une quelconque des revendications 8 à 11 , dans lequel le temps de malaxage est compris entre 2 secondes et 5 minutes. The process for preparing an asphalt mix according to any one of claims 8 to 11, wherein the mixing time is between 2 seconds and 5 minutes.
13. Utilisation d'un additif alkylthiol de formule générale (1) CnH2n+i-SH dans laquelle n représente un entier variant de 18 à 110, dans une composition de liant bitumineux pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou diminuer le temps de malaxage et/ou augmenter la maniabilité dudit enrobé. 13. Use of an alkylthiol additive of general formula (1) C n H2 n + i-SH wherein n represents an integer ranging from 18 to 110, in a bituminous binder composition for reducing the temperatures of manufacture, of setting implement and / or compaction of an asphalt mix and / or reduce the mixing time and / or increase the workability of said asphalt.
14. Utilisation d'une composition de liant bitumineux telle que définie dans les revendications 1 à 4 pour diminuer les températures de fabrication, de mise en œuvre et/ou de compactage d'un enrobé bitumineux et/ou améliorer le temps de malaxage et/ou la maniabilité dudit enrobé.  14. Use of a bituminous binder composition as defined in claims 1 to 4 to reduce the temperatures of manufacture, implementation and / or compaction of a bituminous mix and / or improve the mixing time and / or the workability of said mix.
15. Utilisation d'un enrobé selon la revendication 7, pour la fabrication de revêtements de routes, de chaussées, de trottoirs, de voiries, d'aménagements urbains, de sols, d'étanchéité de bâtiments ou d'ouvrages, en particulier pour la fabrication en application routière, de couches de fondation, de couches de base, de couches d'assise, de couches de surface telles que les couches de liaison et/ou les couches de roulement.  15. Use of an asphalt mix according to claim 7, for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, floors, waterproofing of buildings or structures, particularly for the manufacture in road application, foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.
EP13814100.7A 2012-12-21 2013-12-18 Bituminous binder composition for producing surfacing materials at low temperatures Withdrawn EP2935442A1 (en)

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FR1262612A FR3000091B1 (en) 2012-12-21 2012-12-21 BITUMINOUS BINDER COMPOSITION FOR THE PREPARATION OF LOW TEMPERATURE COILS
PCT/EP2013/077082 WO2014095995A1 (en) 2012-12-21 2013-12-18 Bituminous binder composition for producing surfacing materials at low temperatures

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