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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
  • C04B26/26—Bituminous materials, e.g. tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
  • C08L95/005—Aqueous compositions, e.g. emulsions
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients

Definitions

• the present invention relates to cold bituminous mixes comprising one or more polymerized fatty acids.
• the cold bituminous mixes according to the invention are, for example, bituminous grouts, cold-cast asphalts, low-emulsions, cold bituminous concretes.
• the invention also relates to the process for preparing these cold bituminous mixes.
• the invention also relates to the use of these cold bituminous mixes in road applications for the manufacture of new pavements, for the reinforcement or the maintenance of old pavements or their occasional repair.
• bituminous coatings In the field of the road industry, two techniques for preparing bituminous coatings coexist: the so-called “hot” techniques, in which the bitumen is brought to relatively high temperatures, and the so-called “cold” techniques, based on the use of aqueous bitumen emulsions at lower temperatures.
• the surface coatings are prepared from an aqueous emulsion of bitumen on which are placed aggregates.
• the bitumen emulsion is applied to the surface to be coated by a spreader; the aggregates are then applied by a chip to the bitumen emulsion, the assembly is finally compacted.
• the emulsions used for surface coatings are fast-breaking emulsions because the bitumen emulsion must break almost immediately after contact with the aggregates.
• the rupture index of an emulsion is measured according to standard NF EN 13075-1. For superficial coatings, the rupture index is generally less than or close to 100 grams of fine for 100 grams of emulsion.
• Cold mixes are prepared by mixing (or mixing) aggregates with an emulsion of bitumen.
• bitumen emulsion When mixing the bitumen emulsion with the aggregates in the mixer, the bitumen emulsion must not break. It is therefore impossible to use a fast-breaking emulsion as in superficial coatings. For example, the mixing time without rupture is typically between 40 seconds and 90 seconds for the cold-cast mixes.
• a cold mix must meet two antinomic objectives: a break sufficiently delayed to prevent breakage in the mixer (typically more than 40 seconds for cold mixes), but then, after application on the pavement, very fast for allow an opening to the fast traffic. This contradictory specification makes the formulation of cold mixes difficult.
• bitumens that are rare and expensive. It is mainly naphthenic bitumens, in particular naphthenic bitumens with natural acidity. These bitumens have both a kneading time without breaking and a rise in cohesion suitable in particular cold-mix asphalt.
• the object of the present invention is to provide a cold bituminous mix, especially a cold-cast mix, which can be kneaded without breaking for a few tens of seconds, preferably for at least 40 seconds.
• Another object of the invention is to provide a cold bituminous mix, in particular a cold-cast asphalt, having a rapid cohesion and hardening in order to allow rapid re-rolling.
• Another object of the invention is to provide a bituminous cold mix with good mechanical strength.
• the asphalt once put under circulation, must in particular withstand the aggressions caused by the tires of the vehicles.
• the invention relates to a cold bituminous mix obtained by mixing aggregates with a bitumen emulsion, said mix comprising one or more polymerized fatty acids.
• the polymerized fatty acids comprise fatty acid monomers, fatty acid dimers, fatty acid trimers and fatty acid tetramers, preferably comprising predominantly fatty acid dimers and dimer trimeres. 'Fatty acids.
• the polymerized fatty acids are unsaturated fatty acids of 18 carbon atoms, in particular chosen from oleic acid, linoleic acid and linolenic acid, taken alone or as a mixture.
• the polymerized fatty acids comprise at least 20% by weight of fatty acid dimers and at least 3% by weight of fatty acid trimers.
• the molar mass of the polymerized fatty acids is between 500 g.mu 1 and 1000 g mol -1 , more preferably between 600 g mol -1 and 800 g mol -1 .
• the bituminous mix cold comprises from 0.1 to 5% by weight of polymerized fatty acids relative to the amount of bitumen, preferably from 0.5 to 2% by weight.
• the bitumen has a penetrability measured according to EN 416, between 10 and 300, preferably between 20 and 200, more preferably between 50 and 100.
• the bitumen emulsion comprises from 50 to 70% by weight of bitumen with respect to the amount of bitumen emulsion, preferably from 55 to 65%.
• the bitumen emulsion further comprises at least one surfactant, in an amount of preferably from 0.1% to 5% by weight relative to the amount of bituminous emulsion, preferably from 0.5% to 3%, preferably 1% to 2%.
• the granules preferably have a particle size of between 0/2 and 4/6 mm.
• the cold bituminous mix additionally comprises fines.
• the bitumen emulsion has a fracture index measured according to standard NF EN 13075 greater than or equal to 100 g / 100 g of emulsion, preferably greater than or equal to 140 g / 100 g of bitumen emulsion, and preferably less than 250 g / 100 g of bitumen emulsion or still less than 200 g / 100 g of bitumen emulsion.
• the cold bituminous mix is chosen from bituminous grouts, cold-cast asphalts, low-emulsions, cold-drawn bituminous concretes, preferably cold-cast asphalts.
• the cold-cast mix has a breaking time after mixing greater than 40 seconds measured according to the standard NF EN 12274-4, preferably between 45 and 120 seconds.
• the cold-cast mix has a rise in cohesion measured according to the standard NF EN 12274-4 greater than or equal to 0.9 Nm, preferably greater than or equal to 1.1 Nm, more preferably greater than or equal to 1 , 3 Nm and preferably less than 2 Nm, or even less than 1, 5 Nm
• the cold-cast mix has an abrasion resistance measured according to standard NF EN 12274-5 less than or equal to 25 g / m 2 , preferably less than or equal to 5 g / m 2 , more preferably lower or equal to 2.5 g / m 2 and preferably greater than or equal to 0.5 g / m 2 , preferably greater than or equal to 1 g / m 2 .
• the invention also relates to a process for the preparation of cold bituminous mix comprising:
• step (ii) the preparation of an emulsifying solution, - (iii) the mixing of the bitumen of step (i) and the emulsifying solution of step
• step (iv) mixing the bitumen emulsion obtained in step (iii) with aggregates, said process comprising the addition of one or more polymerized fatty acids in one or more of steps (i) to (iv).
• the process for the preparation of cold bituminous mixes, in particular cold-cast asphalts contains the characteristics of polymerized fatty acids, bitumen, bitumen emulsion, aggregates, cold bituminous mixes, cast asphalts cold, defined above.
• the invention finally relates to the use of one or more polymerized fatty acids in the preparation of cold bituminous mixes, in particular cold-cast asphalts as defined above.
• the invention relates to bituminous cold mixes based on bitumen, aggregates and polymerized fatty acids.
• Cold asphalt or cold-coated or cold-rolled cold-mix asphalt is any mixture obtained by kneading an emulsion of bitumen and aggregates.
• Cold mixes are defined in standard NF P 98-149. They are divided into two categories: non-storable mixes and storable mixes. Examples of non-storable cold mixes are bituminous grouts, cold-mix asphalt, low-emulsion and cold bituminous concrete.
• ECF Cold-poured asphalt
• BBF Cold bituminous concrete
• Serious-emulsion are they, defined in the standard NF P 98-121.
• emulsion means a heterogeneous system with two or more liquid phases, consisting of a continuous liquid phase and at least a second liquid phase, dispersed in the first, in the form of fine droplets.
• Bitumen emulsion means an aqueous dispersion of bitumen optionally comprising one or more additives, surfactants, emulsifiers, viscosifiers, thickeners, fluxing agents, plasticizers and / or any other additive making it possible to adjust the properties of the emulsion.
• the bitumen emulsion according to the invention is of anionic or cationic type.
• the bitumen emulsion is preferably cationic. It may include surfactants, such as alkylamine derivatives, mixtures of alkylamidopolyamines and quaternary ammonium salts, or alkylpropylenepolyamine compounds such as N-tallowpropylenepolyamines.
• the bitumen emulsion comprises from 0.1% to 5% by weight of surfactant, preferably from 0.5% to 3%, more preferably from 1% to 2%.
• the polymerized fatty acids are acids derived from the polymerization of the side chains of at least one unsaturated fatty acid.
• the unsaturated fatty acids which make it possible to obtain the polymerized fatty acids are unsaturated fatty acids containing from 4 to 24 carbon atoms (C 4 to C 24 ), preferably from 11 to 22 carbon atoms (Cu to C 22 ), from preferably 16 to 18 carbon atoms (C 16 to C 8).
• unsaturated fatty acids which make it possible to obtain the polymerized fatty acids
• C 8 gadoleic acid (C 20 ), gondoic acid (C 20 ), cetoleic acid (C 22 ), erucidic acid (C 22 ), brassic acid (C 22 ), nervonic acid (C 24 ), tiglic acid (C5), sorbic acid (C 6 ), linoleic acid (Ci 8 ), hiragonic acid (Ci ⁇ ), linolenic acid (Ci 8 ), ⁇ -linolenic acid (Ci 8 ), eléostéarique acid (Ci 8 ), parinaric acid (Ci 8 ), homo- ⁇ -linolenic acid (C 20 ), arachidonic acid (C 20 ), clupanodonic acid (C 22 ) alone or in mixtures.
• the unsaturated fatty acids are unsaturated fatty acids of 18 carbon atoms -C 8, especially chosen from oleic acid, linoleic acid, linolenic acid alone or in mixture.
• the reaction for polymerizing the fatty acid chains is a Diels-Alder reaction (for more information see Kirk Othmer Encyclopedia of Chemical Technology, Vol 7, p.776 or "The dimer acids", Humko Sheffield, 1975).
• the polymerization reaction is a dimerization, trimerization or tetramerization reaction in which fatty acid dimers (or diacid dimers), fatty acid trimers (or triacid trimers) or tetramers of fatty acids (or tetrameric tetracids). Traces of unreacted fatty acids may also be present (or fatty acid monomers).
• polymerized fatty acids comprising unreacted fatty acids (fatty acid monomers), fatty acid dimers, fatty acid trimers and tetramers of fatty acids are obtained. acids to different concentrations.
• the polymerized fatty acids mainly comprise fatty acid dimers and fatty acid trimers. Unreacted fatty acids (fatty acid monomers) or tetramers of fatty acids are minor products.
• the polymerized fatty acids comprise at least 20% by weight of fatty acid dimers and at least 3% by weight of fatty acid trimers. More preferably, the polymerized fatty acids comprise at least 75% by weight of fatty acid dimers and at least 15% by weight of fatty acid trimers.
• polymerized fatty acids include the Pripol ® marketed by Uniqema, the POLYMERGIN ® marketed by Harburger Brinckman & Mergell GmbH, the DIMER ® marketed by Westvaco, the EMPOL ® marketed by Cognis.
• EMPOL 1008 ® comprises 3.5% by weight of unreacted C1 8 fatty acid, 92.3% by weight of C 36 fatty acid dimer and 3.5% by weight of trimer fatty acid C 5 4.
• Empol ® 1018 comprises 4% by weight of fatty acid unreacted, 79% by weight of fatty acid dimer and 17% by weight of trimer 'fatty acid.
• EMPOL 1040 ® comprises 20% by weight of C 6 fatty acid dimer and 80% by weight of C 5 4 fatty acid trimer.
• EMPOL 1041 ® comprises 10% by weight of dimer fatty acid C 36 and 90% by weight of trimer fatty acid C 54.
• EMPOL 1054 ® comprises 4% by weight of fatty acid Ci 8 unreacted, 55% by weight of dimer fatty acid C 36 and 35% by weight fatty acid trimer in C 54 .
• Pripol ® 1045 comprises 10% by weight of dimer fatty acid C 36 and 90% by weight of trimer fatty acid C 54.
• Pripol ® 1040 comprises 0.1% by weight fatty acid monomer, 22.5% by weight of fatty acid dimer and 77% by weight of trimer fatty acid.
• Pripol ® 1017 comprises 2% by weight fatty acid monomer, 79% by weight of fatty acid dimer and 19% by weight of trimer fatty acid.
• Pripol ® 1012 comprises 0.1% by weight fatty acid monomer, 97% by weight of dimer fatty acid and 1.1% by weight of trimer fatty acid.
• Pripol ® 1013 comprises about 0.1% by weight fatty acid monomer, 97% by weight of dimer fatty acid and 3% by weight of trimer fatty acid.
• the molar mass of the polymerized fatty acids is between 500 g.mol -1 and 1000 g mol -1 .
• the average molar mass of the polymerized fatty acids is between 600 g.mol -1 and 800 g mol -1 .
• bitumens used in the invention are bitumens from different origins. We can first mention bitumen of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands.
• bitumens according to the invention are also 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 bitumens may be hard grade or soft grade bitumens. The different bitumens obtained by the refining processes can be combined with one another to obtain the best technical compromise.
• bitumens used may also be fluxed bitumens by addition of volatile solvents, petroleum fluxes, carbochemical fluxes and / or fluxes of vegetable origin.
• Polymer modified bitumens can also be used.
• a polymer mention may be made, for example, and in an indicative and nonlimiting manner, thermoplastic elastomers such as styrene and butadiene random or block copolymers, linear or star (SBR, SBS) or styrene and isoprene (SIS ), optionally crosslinked, copolymers of ethylene and of vinyl acetate, olefinic homopolymers and copolymers of ethylene (or propylene or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinyl chloride, rubber crumbs or any polymer used for the modification of bitumens and mixtures thereof.
• a quantity of polymer of 2 to 10% by weight relative to the weight of bitumen is used.
• bitumens also called clear, pigmentable or colorable bitumens. These bitumens contain little or no asphaltenes and can therefore be colored. These synthetic bitumens are based on petroleum resin and / or indene-coumarone resin and lubricating oil as described, for example, in EP1 79510.
• bitumen is a bitumen of penetrability measured according to the EN1426 standard of between 10 and 300, preferably between 20 and 200, more preferably between 50 and 100.
• the bitumen emulsion comprises between 50 and 70% by weight of bitumen, more preferably between 55 and 65%, even more preferentially around 60%.
• the aggregates that can be used according to the invention are of various origins. These are aggregates from quarries or gravel pits, recycling products such as aggregates from old asphalt milling, manufacturing scrap, materials from the recycling of building materials, slags, shales, taken alone or mixed.
• the aggregates used are road aggregates, meeting the relevant standards: NF EN 13043 in Europe and ASTM C33 in the United States of America.
• aggregates of the Meilleraie type (porphyry diorites of siliceous nature, which can be assimilated to an SiO 2 / CaO mixture 60/40% by weight) are used.
• the granulometry of the aggregates is between 0/2 mm and 0/10 mm.
• the aggregates according to the invention may also contain fines, that is to say small aggregates passing through a sieve of 0.08 mm. It is also possible to add to the aggregates special fines such as cement or lime.
• the cold mixes obtained according to the invention have a good index of rupture.
• the rupture indices measured according to standard NF EN 13075, are greater than or equal to 100 g / 100 g of emulsion, preferably greater than or equal to 140 g / 100 g of emulsion, so that the emulsions according to invention do not break too fast.
• the cold-cast mixes according to the invention have a non-breaking mixing time greater than 40 seconds measured according to standard NF EN 12274-4, which allows an easy implementation.
• the cold-poured mixes according to the invention have a good cohesion increase.
• the cohesive increases measured according to standard NF EN 12274-4 are greater than or equal to 0.9 Nm, preferably greater than or equal to 1.1 Nm, more preferably greater than or equal to 1.3 Nm, which allows reopening to traffic under a short time.
• the cold-cast mixes according to the invention have a good resistance to abrasion.
• the abrasion resistance measured according to standard NF EN 12274-5 is less than or equal to 25 g / m 2 , preferably less than or equal to 5 g / m 2 , more preferably less than or equal to 2.5 g / m 2. m 2 , which guarantees a good mechanical resistance of the mixes.
• the process for preparing cold bituminous mixes according to the invention comprises the conventional steps of the preparation of cold mixes, namely the steps of: - (i) supplying a bitumen, (ii) preparation of an emulsifying solution,
• step (iii) mixing the bitumen of step (i) and the emulsifying solution of step (ii)
• step (iv) mixing the bitumen emulsion obtained in step (iii) with aggregates.
• the introduction of fatty acids into the preparation of cold bituminous mixes according to the invention is essential.
• the polymerized fatty acids are introduced indifferently at one of the stages (i) to (iv), that is to say in the bitumen alone (i), in the emulsifying solution (ii), during the emulsification bitumen (iii) or when mixing with aggregates (iv). It could also be envisaged to introduce the polymerized fatty acids in several of the steps (i) to (iv), for example in the bitumen alone and then when it is emulsified.
• the polymerized fatty acids are added to the bitumen alone of step (i), prior to the preparation of the bitumen emulsion of step (iii). More preferably, 0.1 to 5% by weight of polymerized fatty acids, preferably 0.5 to 2% by weight, preferably 0.7 to 1% by weight, are added to the bitumen.
• the products used according to the invention are the products below:
• the polymerized fatty acids are the polymerized fatty acids AG3 to AG6, identified in Table 1 below.
• bitumen used is a bitumen derived from a paraffinic crude oil, of penetrability 89, measured according to EN 1426, respectively for bituminous compositions CB2 to CB6, bituminous emulsions EB2 to EB6 and cold-cast asphalts ECF2 at ECF6.
• bitumen used is a bitumen from a crude oil of naphthenic nature, penetrability 86, measured according to EN 1426, for bituminous composition CBl, emulsion bitumen EB1 and cold mix asphalt ECFl.
• the surfactant used is Redicote E 1 1 HF.
• the thickener (or viscosity adjuster) used is the Réholate 255.
• the aggregates are silico-limestone Meilleraie.
• the granulometry of the aggregates is as follows: 30% 0/2, 50% 2/4, 20% 4/6.
• the cement used is Portland type.
• bituminous compositions according to the invention CB3 to CB6 (bitumen and polymerized fatty acids) and two control bituminous compositions CB1 and CB2 are prepared:
• the bituminous composition CB1 is not additive with polymerized fatty acids, it corresponds to 100% of the bitumen from a crude oil of naphthenic nature, penetrability 86, measured according to EN 1426.
• the bituminous composition CB2 is not additive with polymerized fatty acids, it corresponds to 100% of a bitumen from a paraffinic crude oil, penetrability 89, measured according to EN 1426.
• the CB3 to CB6 bituminous compositions are prepared from paraffinic bitumen of penetrability 89 above, to which are added the polymerized fatty acids ACG3 to ACG6.
• bituminous compositions CB3 to CB6 For bituminous compositions CB3 to CB6, the bitumen (99.3% by weight) and the polymerized fatty acids (0.7% by weight) are mixed in a mixer at 160 ° C. for one hour, at the end of which gets a homogeneous mixture.
• An emulsifying solution is then prepared by mixing with water, 1.6% by weight of surfactant, 0.1% by weight of thickener and 0.15% by weight of HCl.
• the emulsifying solution is heated to a temperature of 20 to 120 ° C, preferably 40 to 80 ° C.
• bitumen emulsion is then prepared by mixing 60% by weight of bituminous composition at 140-150 ° C. and 40% by weight of emulsifying solution at 40-50 ° C.
• the bitumen is dispersed by mechanical energy input, for example in a colloid mill or a turbine.
• bitumen composition content of the emulsion - Bitumen composition content of the emulsion.
• pH of the emulsion measured according to standard NF EN 12850.
• the rupture index represents the amount of fines to be added to break 100 g of emulsion.
• 500 ⁇ m sieve deposition measured according to standard NF EN 1429.
• a certain amount of emulsion is passed through a 500 ⁇ m sieve and the particles which do not pass through the sieve are collected. This gives an indication of the quality of the emulsion, the lower the particle content, the finer the emulsion.
• bitumen emulsions obtained thus have good characteristics. Indeed, the sieve deposit is particularly low and the rupture rate quite satisfactory since the amount of fines to be introduced to break the emulsion is between 141 grams and 171 grams, which means that the emulsion is not a fast-breaking emulsion, the amount of fines to bring to break the emulsions is important.
• bitumen emulsion as defined above.
• ECF3 to ECF6 have, as the ECF1 and ECF2 controls, a mixing time without breaking greater than 40 seconds which allows a correct implementation.
• ECF3 to ECF6 exhibit a cohesion increase 30 minutes higher than that of the ECF2 control and an abrasion resistance greater than that of the ECF2 control.
• the addition of the polymerized fatty acids allows a faster reopening of the traffic than a cold-cast mix without polymerized fatty acids.
• the addition of the polymerized fatty acids increases the mechanical strength of the cold-cast mixes compared with the cold-cast mixes without polymerized fatty acids.
• the cold-poured mixes ECF4 and ECF5 have a cohesion at 30 minutes of 1.3 Nm, equivalent to that of the control ECF1 (1.4 Nm), which ensures a rapid increase in cohesion to allow reopening at traffic in a very short time.
• the cold-cast asphalts ECF5 and ECF6 have an abrasion resistance equivalent to that of the ECFl control, which guarantees a very good mechanical strength.

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