EP3841163A1

EP3841163A1 - Thermoreversible bituminous composition

Info

Publication number: EP3841163A1
Application number: EP19782651.4A
Authority: EP
Inventors: Manuel MERCE; Laurent Bouteiller; Sandrine PENSEC; Thomas COUSTHAM
Original assignee: Total Marketing Services SA; Sorbonne Universite
Current assignee: Sorbonne Universite; TotalEnergies Onetech SAS
Priority date: 2018-08-22
Filing date: 2019-08-19
Publication date: 2021-06-30
Also published as: FR3085169B1; US20210324175A1; FR3085169A1; CA3109575A1; WO2020039139A1

Abstract

The present invention relates to bituminous compositions comprising at least one molecule of general formula (I) or (II), alone or in a mixture. The invention also relates to the use of these bituminous compositions in the fields of road applications, particularly in the production of road binders and roadways in general, as well as in the fields of industrial applications. The invention also relates to a method for preparing said bituminous compositions. The invention further relates to novel molecules of formula (I) or (II), alone or in a mixture, which can be used in particular in the formulation of bituminous compositions.

Description

HEAT-REVERSIBLE BITUMINOUS COMPOSITION

TECHNICAL AREA

The present invention belongs to the field of bitumens. A first aspect of the invention relates to new bituminous compositions comprising new molecules. These bituminous compositions are hard and have a good consistency at use temperatures and a viscosity similar to that of conventional bitumens of the same grade at application temperatures. In particular, the invention relates to said solid compositions and in divided form at room temperature

The invention also relates to a process for the preparation of these bituminous compositions, in particular when they are solid and in divided form at room temperature, and their use in the fields of road applications, in particular in the manufacture of road binders, mixes and pavements in general, and in the fields of industrial applications.

The present invention also relates to a process for the manufacture of mixes from bituminous compositions according to the invention, as well as a method of transport and / or storage and / or handling of said bituminous compositions, in particular at high ambient temperature.

The invention also relates to new molecules which can be used in particular in the formulation of bituminous compositions, preferably in the form of solid bituminous compositions and in divided form at room temperature.

TECHNICAL BACKGROUND

Bitumen or bituminous binder is the main hydrocarbon binder used in the field of road construction or civil engineering. To be able to be used as a binder in these different applications, the bitumen must have certain physico-chemical and mechanical properties. It must in particular be sufficiently hard and have a good consistency at the temperatures of use to avoid, for example, the formation of ruts caused by traffic. Bitumen must also be elastic to resist deformations imposed by traffic and / or temperature changes, phenomena which lead to cracking of asphalt or tearing of surface aggregates. Finally, the bitumen must be sufficiently fluid at the lowest possible application temperatures to allow for example a good coating of the aggregates and the installation of the asphalt on the road. The implementation of a binder Bituminous therefore requires combining hardness, consistency and even the elasticity of bitumen at use temperatures and a low viscosity at application temperatures.

Since bitumen alone is not generally elastic enough, polymers are added to the bitumen which can be optionally crosslinked. These crosslinked polymers provide bituminous compositions with markedly improved elastic properties. However, cross-linking is generally irreversible: once cross-linking has been carried out, it is not possible to return to the initial state existing before the cross-linking reaction. The crosslinked bituminous compositions thus have good elastic properties, but the viscosity of these is very high. One of the drawbacks associated with this high viscosity is the need to heat the crosslinked bitumen to an application temperature higher than that of an uncrosslinked bitumen, which increases energy costs and requires the use of additional protections for operators. .

Depending on the intended applications, it is necessary to find the right compromise between mechanical properties including elasticity, hardness, consistency, fluidity and viscosity, in particular the hot viscosity of the binder.

Another problem in the use of bitumen is related to its transport, handling and storage. In general, bitumen is stored and transported hot, in bulk, in tankers or by ships at high temperatures in the range of 120 ° C to 180 ° C. However, the storage and transport of hot bitumen has certain drawbacks. The transport of hot bitumen in liquid form is considered dangerous and it is highly regulated from a regulatory point of view. This mode of transport does not present any particular difficulties when the transport equipment and infrastructure are in good condition. Otherwise, it can become problematic: if the tanker is not sufficiently insulated, the viscosity of the bitumen may increase during a journey that is too long. Bitumen delivery distances are therefore limited. On the other hand, keeping bitumen at high temperatures in tanks or in tankers consumes energy. In addition, keeping the bitumen at high temperatures for a long time can affect the properties of the bitumen and thus change the final performance of the mix.

To overcome the problems of transport and storage of hot bitumen, packaging allowing the transport and storage of bitumen at room temperature has been developed. This mode of transport of bitumen in packaging at room temperature represents only a small fraction of the quantities transported in the world, but it corresponds to very real needs for geographic regions of difficult and costly access by traditional means of transport. US 3,026,568 describes bitumen granules covered with a powdery material, such as limestone powder. However, this type of bitumen in granules does not prevent the creep of the bitumen, in particular at high ambient temperature.

Application WO 2008107551 describes a reversible mode of crosslinking of bituminous compositions based on the use of organogelling additives. The thermoreversible crosslinked bituminous compositions thus obtained are hard at use temperatures and have a reduced viscosity at application temperatures.

Application WO 2009/153324 describes bitumen granules coated with a polymeric anti-caking compound, in particular polyethylene. The disadvantage of this coating is that it modifies the properties of the bitumen during its road application.

Application WO 2016/016318 describes bitumen granules comprising a chemical additive. These bitumen granules allow the transport and / or storage and / or handling of the bitumen at room temperature without it leaking, as well as the reduction of their adhesion and agglomeration between them.

Application US 2987515 describes urethane derivatives comprising cyclic amidine groups as well as their preparation process.

In continuation of its work, the Applicant has surprisingly discovered a new bituminous composition comprising at least one bitumen and at least one molecule of general formula (I) or (II) or their mixture. The bituminous compositions thus developed have the advantage that they have good hardness and good consistency at temperatures of use, satisfactory mechanical properties, in particular good elasticity, and that they exhibit, at application temperatures, a viscosity similar to that of conventional bitumens of the same grade.

The bituminous compositions according to the invention have the advantage that they are solid at room temperature and allow the shaping of the bitumen in divided form, in particular in the form of granules or breads. These bituminous compositions which are solid at room temperature and in divided form also make it possible to avoid, reduce and / or delay the adhesion and agglomeration of the granules or breads during their transport and / or storage and / or handling at temperature. ambient, especially at high ambient temperature, over long periods, compared to bitumen-based materials of the prior art. These bituminous compositions which are solid at room temperature and in divided form retain their properties over time. OBJECTIVES OF THE INVENTION

Under these circumstances, the objective of the present invention is to propose new bituminous compositions comprising the molecules of general formula (I) or (II) as defined below, or their mixtures.

Another objective of the invention is to provide bituminous compositions having good physicochemical and mechanical properties at use temperatures, in particular in terms of hardness, consistency, or even elasticity, but also having at temperatures of application, preferably a reduced viscosity, even equivalent to that of a non-additive bitumen.

Another objective of the invention is to propose a simple process for the preparation of bituminous compositions comprising said molecules of general formula (I) or (II) or their mixture.

Another objective of the invention is to provide bituminous compositions which are solid at room temperature and which allow bitumen to be shaped in divided form, in particular in the form of granules or breads.

Another objective of the invention is to provide bituminous compositions which are solid at room temperature and in divided form having good hardness and good consistency at use temperatures without degrading the mechanical properties of the bitumen. In particular, the aim is to obtain compositions having a viscosity similar to that of standard bitumens of the same grade at application temperatures.

Another objective of the invention is to provide bituminous compositions which are solid at room temperature and in divided form, making it possible to avoid and reduce and / or delay the adhesion and agglomeration of the granules or breads during their transport. and / or storage and / or handling at ambient temperature, in particular at high ambient temperature, over long periods while retaining their properties over time.

Another objective of the invention is to propose new molecules capable in particular of forming a thermoreversible network in bituminous compositions.

BRIEF DESCRIPTION

The invention relates to a bituminous composition comprising at least one bitumen and at least one molecule of general formula (I) or (II) or a mixture thereof:

or :

- Rci represents a hydrocarbon chain comprising from 2 to 26 carbon atoms, and optionally one or more heteroatoms,

- R _C 2 represents a hydrocarbon chain comprising from 2 to 26 carbon atoms, and optionally one or more heteroatoms,

- R _A and R _b, identical or different, represent a hydrocarbon group comprising from 4 to 200 carbon atoms, and optionally comprising one or more heteroatoms,

- X and X ’, identical or different, represent a chemical function chosen from urethane, urea, amide, hydrazide or oxamide functions,

- m and n are whole numbers between 0 and 25,

when the composition comprises only one of the molecules (I) and (II), m and n are whole numbers between 1 and 25,

when the composition comprises a mixture of molecules (I) and (II), one of the integers m and n can be equal to 0.

Preferably, Rci and Rc _{2, which may be} identical or different, represent a linear, saturated, aliphatic, hydrocarbon chain.

Preferably, Rci and Rc ₂ , identical or different, represent a hydrocarbon chain comprising from 2 to 18 carbon atoms, preferably from 2 to 12 carbon atoms, preferably from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, preferably from 4 to 8 carbon atoms.

In a particular embodiment of the invention, R _Ci and Rc _¾ identical or different are chosen from the groups -C ₄ H _8- , -C ₅ H _I0 -, -C ₆ H _I2 -, -C ₇ H _I4 -, -C _S H _I6- , preferably from the groups -C ₄ H _8- , -C ₆ H _I2 -, -C _S H _IÔ -.

In a variant according to the invention, R _A and R _{B, which are} identical or different, represent a hydrocarbon chain comprising from 4 to 150 carbon atoms or an oligomer soluble in the bitumen chosen from polyolefins, polyetheroxides, polyacrylates, polymethacrylates, polysulfids, polystyrenics, polybutadienes, polyisobutenes, polyisoprenes, polyesters, polyamides, polysiloxanes, polyvinyl chlorides (PVC), polytetrafluoroethylenes (PTFE).

Advantageously, R _A and R _{B, which are} identical or different, represent a hydrocarbon chain chosen from octadecyl, oleyl, hexadecyl, tetradecyl, pentadecyl, heptadecyl, cicosylc, dodecyl, tridecyl, the undécylc.

Preferably, X and X ’, identical or different, represent a urethane or urea function.

Preferably, X and X ’are identical and represent a urethane function.

The bituminous composition according to the invention advantageously comprises from 0.1 to 30% by mass of molecule of general formula (I) or (II) or their mixture, preferably from 0.5 to 20%, preferably from 1 to 10%, more preferably from 2 to 10%, preferably from 1.5 to 5%, even more preferably from 2 to 5%, by mass relative to the total mass of the bituminous composition.

The invention also relates to the use of at least one molecule according to the invention corresponding to general formula (I) or (II) or their mixture, to prepare bituminous compositions, advantageously bituminous compositions in solid form at room temperature and in divided form.

The invention relates in particular to a process for preparing a bituminous composition which comprises the following stages:

- the supply of a bituminous binder comprising at least one bitumen,

- bringing the molecule of general formula (I) or (II) into contact, or mixing them, at a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C, preferably between 110 and 180 ° C with the bituminous binder, then optionally

- The shaping of the bituminous composition in divided form, and in particular in the form of breads or granules.

Preferably, the bitumen is chosen from bitumens of natural origin, from bitumens obtained from the refining of crude oil such as atmospheric distillation residues, vacuum distillation residues, visbreaked residues, blown residues, their mixtures and their combinations or among synthetic bitumens.

The invention also relates to a solid bituminous composition at room temperature and in divided form.

According to a preferred embodiment, said bituminous composition is in the form of granules or breads. Another aspect of the invention relates to a method of transport and / or storage and / or handling of said bituminous composition, said bituminous composition being transported and / or stored and / or handled at room temperature in divided and solid form, in particular in the form of breads or solid granules.

The invention also relates to the use of the solid bituminous composition at ambient temperature and preferably in divided form in the fields of road applications, in particular in the manufacture of road binders, mixes and roadways in general, and in the fields of industrial applications.

Finally, the invention relates to a molecule corresponding to the general formula (I) or (II) as defined above and in detail below, or their mixture, and their use for preparing a bituminous composition, in particular for preparing a solid bituminous composition at room temperature and in divided form.

The invention also relates to a molecule chosen from those corresponding to the following formulas:

The invention also relates to the use of bituminous compositions as defined above and in detail below, in the fields of road applications, optionally in admixture with aggregates or aggregates of recycled bituminous mixes, in particular for manufacturing a surface coating, a hot mix, a cold mix, a mix cold-cast, a severe emulsion, a base layer, a bonding layer, a bonding layer, a wearing course, an anti-corrosion layer, a draining mix, or an asphalt, and in the fields of industrial applications , in particular for preparing a waterproofing coating, a membrane or an impregnation layer.

DETAILED DESCRIPTION

The expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all the values going from X to Y.

By "oligomer" is meant a macromolecule made up of a limited number of repeating units. These repeat units can all be the same or an oligomer can comprise different repeat units. Generally an oligomer comprises from 2 to 100 repeat units and an average molar mass greater than or equal to 200 g / mol and less than or equal to 20,000 g / mol, preferably less than or equal to 10,000 g / mol.

The bituminous composition according to the invention and its preparation process

Bituminous composition

The bituminous compositions according to the invention comprise at least one bitumen and at least one molecule of general formula (I) or (II) or their mixture:

or :

- Rci represents a hydrocarbon chain comprising from 2 to 26 carbon atoms, and optionally one or more heteroatoms, - R _C 2 represents a hydrocarbon chain comprising from 2 to 26 carbon atoms, and optionally one or more heteroatoms,

- X and X ', identical or different, represent a chemical function chosen from the urethane functions -0- (CO) -NH-, urea -HN- (CO) -NH-, amide - (CO) -NH-, hydrazide - (CO) - NH-NH- or oxamide -HN- (CO) - (CO) -NH-,

- m and n are whole numbers between 0 and 25,

In a bituminous composition comprising a mixture of molecules (I) and (II) according to the invention, at least one of the integers m and n is different from 0.

By "their mixture" is meant according to the invention the mixtures of molecules (I) and (II) in all proportions.

When Rci and / or Rc ₂ comprise one or more heteroatoms, these are advantageously chosen from O, N and S.

Preferably, Rci and Rc2, identical or different, represent a saturated, linear, aliphatic, hydrocarbon chain.

Preferably, Rci and Rc2, identical or different, represent a hydrocarbon chain comprising from 2 to 18 carbon atoms, preferably from 2 to 12 carbon atoms, preferably from 2 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, preferably from 4 to 8 carbon atoms. For example, Rci and R _C 2, identical or different, represent a hydrocarbon chain comprising 4, 5, 6, 7 or 8 carbon atoms.

In a particular embodiment of the invention, R _Ci and Rc2 _, identical or different, are chosen from the groups -C ₄ H _8- , -C ₅ H _I0 -, -C ₆ H _I2 -, -C ₇ H _I4 -, -C _S H _I6- , preferably from the groups -C ₄ H _8- , -C ₆ H _I2 -, -C _S H _IÔ -.

The identical or different hydrocarbon groups R _A and R _B are advantageously chosen from:

- hydrocarbon chains, aliphatic or aromatic, linear or branched, saturated or unsaturated, acyclic or cyclic, comprising from 4 to 200 carbon atoms and optionally comprising one or more heteroatoms, - oligomers soluble in bitumen comprising from 4 to 200 carbon atoms and optionally comprising one or more heteroatoms.

When R _A and R _B comprise one or more heteroatoms, advantageously these are chosen from O, N, S, Si, and the halogens, in particular F and Cl.

In a variant according to the invention, R _A and R _B, identical or different, represent a hydrocarbon chain, aliphatic or aromatic, linear or branched, saturated or unsaturated, acyclic or cyclic, comprising from 4 to 150 carbon atoms, preferably from 4 to 100 carbon atoms, preferably from 4 to 68 carbon atoms, preferably from 10 to 54 carbon atoms, preferably from 10 to 36 carbon atoms.

Preferably, according to this variant, R _A and R _B , identical or different, represent a hydrocarbon chain comprising from 10 to 36 carbon atoms, more preferably from 16 to 20 carbon atoms.

Advantageously, according to this variant, R _A and R _B , identical or different, represent a hydrocarbon chain chosen from octadecyl, oleyl, hexadecyl, tetradecyl, pentadecyl, heptadecyl, eicosyl, dodecyl , tridecyl, undecyle.

Advantageously, according to another variant, R _A and R _{B which are} identical or different, represent an oligomer soluble in bitumen. Advantageously, according to this variant, R _A and R _b , identical or different, are chosen from polyolefins such as polyethylene (PE), polypropylene (PP), polyethylene butylene (PEB), polyisobutene; polyetheroxides such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethyloxide (PTMO); polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutylacrylate (PABu); polysulfids; polystyrenics such as polystyrene (PS); polybutadienes and polyisoprenes; polyesters such as poly-e-caprolactone (PCL), polylactic acid (PLA); polyamides; polysiloxanes and halogenated polymers such as polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE).

Preferably, X and X ’, identical or different, represent a urethane or urea function. For example X can represent a urea function and X ’a urethane function or vice versa. The two functions X and X ’can be identical and represent a urea function. The two functions X and X ’can be identical and represent a urethane function.

Preferably, X and X ’are identical and represent a urethane function.

The molecule of formula (I) or (II) or their mixture according to the invention can be described as comprising a central segment functionalized by two functions X and X 'chosen among the urea and / or urethane and / or amide and / or hydrazide and / or oxamide and two external segments (R _A , R _B ) connected to the central segment by the functions X and X '.

The central segment is repeated m or n times.

Preferably, m and n are whole numbers and are between 1 and 20, preferably between 2 and 20, and more preferably between 2 and 10, even more preferably between 2 and 5.

Advantageously, the molecule of formula (I) or (II) according to the invention has a molar mass of less than 20,000 g.mof ¹ , preferably between 100 and 10,000 g.mof ¹ . Preferably, the molecule of formula (I) or (II) according to the invention has a molar mass of between 100 and 2000 g.mof ¹ , preferably between 100 and 1000 g.mof ¹ .

The molecules of formula (I) or (II) according to the invention have the advantage of having organogelling properties. By "organogelator" or "organogelator molecule", within the meaning of the invention, is meant a compound capable of establishing an association between several molecules of identical or different chemical structures to form a supramolecular network. In bitumen, these so-called organogelling molecules are capable of establishing physical interactions between them leading to self-aggregation with the formation of a 3D supramolecular network which is responsible for the gelling of bitumen. The stack of organogelling molecules allows the formation of a network of fibrils, immobilizing the molecules of the bitumen. The formation of fibrils can be observed for example by polarized optical microscopy, by scanning electron microscopy (SEM) ...

The molecules of formula (I) or (II) according to the invention comprise a central segment comprising functions capable of creating hydrogen bonds. Said central segment is linked to external segments (R _A , R _B ) making it possible to promote the solubility of the molecule (I) or (II) in the bitumen. At use temperatures, ranging from -20 to 80 ° C, the molecules of formula (I) or (II) bind to each other non-covalently, in particular by hydrogen bonds. These hydrogen bonds are weakened when the bitumen is heated to high temperature. Thus at the temperatures of use, the assembly consisting of a large number of molecules of formula (I) or (II) can be assimilated to a “supramolecular” polymer and gives the thus modified bitumen improved properties. At the temperatures of use, the gelation due to the aggregation of the molecules of formula (I) or (II), causes a thickening of the bituminous medium, leading to an increase in hardness, which allows the bituminous compositions according to the invention are solid at room temperature. The hardness of these additive bituminous compositions, at use temperatures, is increased compared to the non-additive starting bitumen. When the bituminous composition is heated, the interactions between the molecules (I) or (II) are weakened, and the bitumen regains the properties of a non-additive bitumen, the viscosity of the hot bituminous composition becomes again that of the starting bitumen. This phenomenon is also described in the present invention by the terminology "thermoreversible network".

By way of example and without limitation, the following detailed formulas (IA), (IB), (IIA), (IIB), (IIC), (IID) and (IIE) are detailed to illustrate the molecules of formula (I) or (II) according to the present invention:

Formula (IA): R _A = R _B = octadecyl; R _ci = R _C 2 = hexyl; X = X '= urethane; m = 1.

Formula (IB): R _A = R _B = oleyl; R _d = butyl; R _c2 = diphenylmethylene; X = X '= urethane; m = l.

Formula (IIA): R _A = R _B = octadecyl; R _d = R _c2 = hexyl; X = X '= urethane; n = 1.

Formula (IIB): R _A = R _B = Krasol LBH-P2000 ^a® ; R _d = hexyl; R _c2 = butyl; X = X '= urethane; n = 4. ^a = Krasol LBH-P2000 ^® is a polybutadiene sold by the company Cray-Valley.

Formula (IIC): R _A = R _B = Kerocom PIBA ^®b; R = diphenylmethylene; R _c2 = butyl; X = X '= urea; n = 1. ^b = Kerocom PIBA is a polyisobutene marketed by the company BASE.

Formula (IID): R _A = R _B = Kerocom PIBA ^® ; R _d = hexyl; R _c2 = butyl; X = X '= urea; n = 1

Formula (IIE): R _A = R _B = oleyl; R _d = diphenylmethylene; R ^ = butyl; X = X '= urea; n = 1.

Preferably, the bitumen compositions according to the invention essentially consist of:

a) bitumen,

b) one or more compounds of formula (I) and / or (II) as defined above.

According to a first advantageous variant, the granules according to the invention preferably comprise essentially:

a) 70% to 99.9% of bitumen,

b) 0.1% to 30% of compounds of formula (I) and / or (II) as defined above.

According to a second advantageous variant, the granules according to the invention preferably comprise essentially:

a) 70 to 99% bitumen,

b) 0.1% to 30% of compounds of formula (I) and / or (II) as defined above, c) one or more anti-caking agents as defined below,

d) one or more olefinic polymeric adjuvants as defined below.

Process for the preparation of the bituminous composition

The bituminous compositions according to the invention comprise at least one bitumen and at least one molecule of general formula (I) or (II) or their mixture.

The bituminous compositions according to the invention advantageously comprise from 0.1 to 30% by mass of molecule of general formula (I) or (II) or their mixture, preferably from 0.5 to 20%, preferably from 1 to 10%, more preferably from 2 to 10%, even more preferably from 2 to 5% by mass relative to the total mass of the bituminous composition.

The process for preparing the bituminous composition according to the invention advantageously comprises the following steps:

- the supply of a bituminous binder comprising at least one bitumen, - bringing the molecule of general formula (I) or (II) into contact, at a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C, preferably between 110 and 180 ° C with the bituminous binder , then eventually

The term "bituminous binder" means a bitumen alone, and optionally comprising additives such as a polymer and / or a fluxing agent. The bituminous binder can be in anhydrous form or in the form of an emulsion.

In one embodiment, the process for preparing the bituminous compositions according to the invention comprises the following steps:

a) bitumen is introduced into a container fitted with mixing means, and the bitumen is brought to a temperature between 70 and 220 ° C, preferably between 90 and 80 ° C, preferably between 110 and 180 ° C,

b) the molecule of general formula (I) or (II) and optionally additives are introduced, c) the bituminous composition obtained from step b) is heated to a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C, preferably between 110 and 180 ° C, with stirring, until a bituminous composition is obtained, advantageously homogeneous, d) optionally the bituminous composition obtained from step c) is shaped in divided form, and in particular in the form of breads or granules.

Bitumen base

The bituminous compositions according to the invention can contain bitumens originating from different origins. Among the bitumens which can be used according to the invention, mention may be made first of all of the bitumens of natural origin, those contained in deposits of natural bitumen, of natural asphalt or the oil sands and the bitumens originating from the refining of crude oil. The bitumens according to the invention are advantageously chosen from the bitumens originating from the refining of crude oil. The bitumens can be chosen from the bitumens or mixtures of bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches. Bitumens can be obtained by conventional methods of manufacturing bitumens in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumens may be optionally visbreaked and / or deasphalted and / or air-rectified. It is common to carry out vacuum distillation of atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process consequently corresponds to the succession of an atmospheric distillation and a vacuum distillation, the charge feeding the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a charge usually composed of distillates and heavy products from vacuum distillation of atmospheric residues from petroleum distillation. This process makes it possible to obtain a blown, or semi-blown or oxidized or air-rectified or partially air-rectified base. The different bitumens or bitumen bases obtained by the refining processes can be combined together to obtain the best technical compromise. Bitumen can also be recycled bitumen. The bitumens can be hard grade or soft grade bitumens.

Advantageously, the bitumen is chosen from bitumens of natural origin, from bitumens resulting from the refining of crude oil such as atmospheric distillation residues, vacuum distillation residues, visbreaked residues, blown residues, their mixtures and their combinations or among the synthetic bitumens otherwise known as clear binders.

In a particular embodiment according to the invention, the bitumen may also comprise at least one polymer and / or a fluxing agent.

As examples of polymers for bitumen, mention may be made of elastomers such as copolymers SB, SBS, SIS, SBS *, SBR, EPDM, polychloroprene, polynorbomene and optionally polyolefins such as polyethylenes PE, HDPE, polypropylene PP , plastomers such as EVA, EMA, copolymers of olefins and unsaturated carboxylic esters EBA, elastomeric polyolefin copolymers, polybutene of the polybutene type, copolymers of ethylene and of acrylic acid esters, methacrylic or maleic anhydride, copolymers and terpolymers of ethylene and glycidyl methacrylate, ethylene-propylene copolymers, rubbers, polyisobutylenes, SEBS, ABS.

Other additives can also be added to the bitumen according to the invention. They are, for example, vulcanizing agents and / or crosslinking agents capable of reacting with a polymer, when it is an elastomer and / or a plastomer, which can be functionalized and / or which may include reactive sites.

Among the vulcanizing agents, there may be mentioned those based on sulfur and its derivatives, used to crosslink an elastomer at contents of 0.01% to 30% by mass relative to the mass of elastomer.

Among the crosslinking agents, mention may be made of cationic crosslinking agents such as mono or polyacids, or carboxylic anhydrides, esters of carboxylic acids, sulfonic, sulfuric, phosphoric acids, even acid chlorides, phenols, in contents of 0.01% to 30% by mass relative to the mass of polymer. These agents are capable of reacting with the elastomer and / or the functionalized plastomer. They can be used in addition to or in replacement of vulcanizing agents.

According to one embodiment, the bituminous composition according to the invention can also comprise an olefinic polymeric adjuvant.

The olefinic polymer adjuvant is preferably chosen from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers and (b) ethylene / monomer A / monomer B terpolymers:

(a) The ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from random or block, preferably statistical, copolymers of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by mass, preferably from 60% to 95% by mass, more preferably from 60% to 90% by mass of ethylene,

(b) The terpolymers are advantageously chosen from random or block, preferably random, terpolymers of ethylene, of a monomer A and of a monomer B.

The monomer A is chosen from vinyl acetate and C1 to C6 alkyl acrylates or methacrylates.

The monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.

The ethylene / monomer A / monomer B terpolymers advantageously comprise from 0.5% to 40% by mass, preferably from 5% to 35% by mass, more preferably from 10% to 30% by mass of units derived from monomer A and , from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of units originating from monomer B, the remainder being formed from units originating from ethylene.

Advantageously, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene (b), of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a monomer B chosen from acrylate. of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by mass, preferably from 5% to 35% by mass, more preferably from 10% to 30% by mass of units derived from monomer A and, 0.5% to 15% by mass, preferably 2.5% to 15% by mass of units from monomer B, the remainder being formed from units from ethylene.

According to one embodiment, the bituminous composition solid at room temperature and preferably in divided form may comprise from 0.05% to 15% by mass, preferably from 0.1% to 10% by mass, more preferably from 0.5% to 6% by mass of the olefinic polymeric adjuvant relative to the total mass of the bituminous composition according to the invention.

According to a particular embodiment, the bituminous composition which is solid at room temperature and preferably in divided form can also comprise between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4 % and 15% by mass of anti-caking agent relative to the total mass of said granules or of said breads according to the invention.

The term “anti-caking agent” or “anti-caking compound” means any compound which limits, reduces, inhibits, delays, the agglomeration and / or the adhesion of the granules to one another during their transport and / or their storage. at room temperature and which ensures their fluidity during their handling.

Preferably, the anti-caking compound is chosen from: talc; fines generally less than 125 µm in diameter, such as siliceous fines, with the exception of limestone fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular pine; rice husk ash; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, fumed silicas, in particular hydrophobic or hydrophilic fumed silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; hydrated lime; the plaster ; rubber crumb; powdered polymers, such as styrene-butadiene (SB) copolymers, styrene-butadiene-styrene copolymers (SBS), and mixtures of these materials.

Advantageously, G anti-caking agent is chosen from talc; fines generally of diameter less than 125 μm with the exception of limestone fines, such as siliceous fines; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular pine; glass powder; sand such as Fontainebleau sand; silica fumes, in particular hydrophobic or hydrophilic silica fumes; fumed silicas, in particular hydrophobic or hydrophilic fumed silicas; and their mixtures. Shaping the bituminous compositions according to the invention

According to a particular embodiment, the bituminous composition according to the invention is solid at room temperature and in divided form. According to a preferred embodiment, the bituminous composition according to the invention is in the form of granules or breads.

The granules according to the invention are obtained by shaping the bituminous composition according to the invention as described above according to any known method, for example according to the manufacturing method described in document US 3,026,568, document WO 2009/153324 or WO 2012/168380. In particular, the methods described in application WO2018 / 104660 can be used.

According to a particular embodiment, the shaping of the granules can be carried out by draining, in particular using a drum.

Other techniques can be used in the granule manufacturing process, in particular molding, extrusion ...

The bread according to the invention according to the invention can be produced according to any known process, for example according to the manufacturing process described in document US2011 / 0290695.

Solid composition at room temperature and in the form of granules according to the invention

According to one embodiment, the bituminous composition according to the invention is in the form of granules.

The granules according to the invention may have, within the same population of granules, one or more shapes chosen from a cylindrical, spherical or ovoid shape. The granules according to the invention preferably have a cylindrical or spherical shape.

According to one embodiment of the invention, the size of the granules according to the invention is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 3 to 30 mm, even more preferably from 5 at 20 mm. For example, the use of a die makes it possible to control the manufacture of granules of a chosen size. A sieving makes it possible to select granules according to their size.

Preferably, the granules according to the invention have a weight of between 0.1 g and 50 g, preferably between 0.2 g and 10 g, more preferably between 0.2 g and 5 g.

According to another embodiment of the invention, the size of the granules according to the invention is such that the longest average dimension is preferably less than or equal to 20 mm, more preferably less than or equal to 10 mm, even more preferably less than or equal to 5 mm.

According to a particular embodiment, the bituminous composition which is solid at room temperature and in divided form according to the invention, preferably in the form of granules, is coated on at least part of its surface, or even all of its surface, with an anti-caking agent. , preferably of mineral or organic origin, more preferably of mineral origin.

In such a case, the mass of anti-caking agent G covering at least part of the surface of the granules is advantageously between 0.2% and 10% by mass, preferably between 0.5% and 8% by mass, more preferably between 0.5% and 5% by mass relative to the total mass of said granules according to the invention.

Preferably, according to this embodiment, the anti-caking compound covers at least 50% of the surface of the granules, preferably at least 60%, preferably at least 70%, more preferably at least 80% and even more preferably at least 90%.

The anti-caking agent is as defined above in the description. According to a variant, the anti-caking compound used to cover at least part of the surface of the granules is chosen from the molecules of formulas (I) and / or (II), advantageously in the form of powder.

Preferably also, the average thickness of the anti-caking layer is preferably greater than or equal to 20 mhi, more preferably between 20 and 100 mhi.

According to one embodiment of the invention, the anti-caking agent included in the granules can be identical to or different from G anti-caking agent covering at least part of the surface of said granules.

Solid composition at room temperature and in the form of breads according to the invention

According to one embodiment, the bituminous composition according to the invention is in the form of bread. Bread is understood to mean a block of the bituminous composition having a mass of between 0.1 kg and 1000 kg, preferably between 1 kg and 200 kg, more preferably between 1 kg and 50 kg, even more preferably between 5 kg and 35 kg, even more preferably between 10 kg and 30 kg, said block being advantageously parallelepipedic, preferably being a block.

The bread according to the invention preferably has a volume of between 100 cm ³ and 50,000 cm ³ , preferably between 5,000 cm ³ and 25,000 cm ³ , more preferably between 10,000 cm ³ and 30,000 cm ³ , even more preferably between 14,000 cm ³ and 25,000 cm ³ . When the bread according to the invention is handled manually by one person, the mass of said bread can vary from 1 to 20 kg, and from 20 to 50 kg in the case of handling by two people. When handling is carried out by mechanical equipment, the mass of the bread can vary from 50 to 1000 kg.

The bread according to the invention can be manufactured according to any known process, for example according to the manufacturing process described in document US2011 / 0290695.

The bread according to the invention is advantageously packaged with a hot-melt film put in place according to any known process, preferably by a film of polypropylene, of polyethylene or a mixture of polyethylene and polypropylene. The bituminous composition packaged in bitumen bread wrapped in a hot-melt film has the advantage of being ready for use, that is to say that the bitumen bread can be directly heated in the melter or optionally introduced directly in the asphalt mixing unit for the manufacture of asphalt, without unpacking beforehand. The hot-melt film which melts with the bituminous composition according to the invention does not affect its properties.

According to one embodiment, the bread according to the invention can also be packaged in a carton according to any known process.

In particular, the bread according to the invention is packaged in a carton by hot pouring the bituminous composition according to the invention into a carton whose wall of the internal face is silicone-coated and then cooled, the dimensions of the carton being adapted to the weight and / or the volume of the bread according to the invention desired.

When the bread according to the invention is wrapped in a hot-melt film or is packaged in a carton, the Applicant has demonstrated that the deterioration of said hot-melt film or of said carton during transport and / or storage at room temperature and even at room temperature high of said bread did not cause the creep of the bread according to the invention. Consequently, the breads according to the invention retain their initial shape and do not stick together during their transport and / or storage at high ambient temperature despite the fact that the hot-melt film or the cardboard is damaged.

Without wishing to be bound by any theory, the Applicant considers that the absence of creep of the solid bituminous composition at room temperature and in the form of granules or of bread during its transport and / or storage at room temperature, in particular high is due to the formulation of the bituminous composition according to the invention and in particular to the presence of at least one molecule of general formula (I) or (II) or their mixture according to the invention within the bituminous composition. Method for transporting and / or storing and / or handling the solid bituminous composition at room temperature and in divided form according to the invention

The invention also relates to a method of transport and / or storage and / or handling of the bituminous composition, said bituminous composition being transported and / or stored and / or handled at room temperature in divided and solid form, in particular in the form of breads or solid granules.

Preferably, said bituminous composition which is solid at ambient temperature and in divided form according to the invention is transported and / or stored at ambient temperature, in particular at elevated ambient temperature for a period greater than or equal to 2 months, preferably 3 months.

By ambient temperature is meant the temperature at which bitumen is used, it being understood that ambient temperature implies that no heat is supplied other than that resulting from climatic conditions.

Thus, the ambient temperature can reach high values, below 100 ° C during the summer periods, in particular in the geographical regions with hot climate.

Preferably, the ambient temperature is less than 100 ° C. Advantageously, the ambient temperature is from 20 ° C to 50 ° C, preferably from 25 ° C to 50 ° C, preferably from 25 ° C to 40 ° C.

Advantageously, the high ambient temperature is from 40 ° C to 90 ° C, preferably from 50 ° C to 85 ° C even more preferably from 50 ° C to 75 ° C, even more preferably from 50 ° C to 60 ° C.

The bituminous compositions which are solid at room temperature and in divided form according to the present invention are remarkable in that they are solid at room temperature and therefore easy to handle, even at high ambient temperatures. The bituminous compositions which are solid at room temperature and in divided form according to the present invention also allow the transport and / or storage of said granules or breads at ambient temperature under optimal conditions, in particular without creep of said granules or breads during their transport and / or storage, even when the ambient temperature is high and without degrading the properties of said bituminous composition, or even by improving them. Use of the bituminous compositions according to the invention

Various uses of the bituminous compositions according to the invention are envisaged in the fields of road applications, in particular in the manufacture of road binders, mixes and pavements in general, and in the fields of industrial applications.

It is possible to envisage the use of the solid bituminous composition at room temperature, in particular in divided form, according to the invention in various road applications, optionally in admixture with aggregates to produce a surface coating, a hot mix, a cold mix. , a cold-cast mix, a severe emulsion, a base coat, a bonding layer, a bonding layer or a wearing course. These applications are aimed in particular at bituminous mixes as materials for the construction and maintenance of pavement bodies and their coating, as well as for the performance of all road works. Mention may be made of other associations of the bituminous composition and of the aggregate having particular properties, such as anti-omiant layers, draining mixes, or asphalts (mixture between a bituminous binder and aggregates of the sand type).

It is possible to envisage the use of the solid bituminous composition at room temperature, in particular in divided form according to the invention in various industrial applications. In industrial applications, mention may be made of its use for preparing a waterproofing coating, a membrane or an impregnation layer.

The bitumen granules according to the invention are particularly suitable for the manufacture of waterproofing membranes, anti-noise membranes, insulation membranes, surface coatings, carpet tiles or even impregnation layers.

Method of manufacturing asphalt

The invention also relates to a process for the manufacture of mixtures comprising at least the bituminous composition which is solid at room temperature, in particular in the divided form according to the invention and aggregates, or aggregates of recycled bituminous mixes, this process comprising at least the stages of:

- heating the aggregates to a temperature ranging from l00 ° C to l80 ° C, preferably from l20 ° C to l80 ° C,

- mixing of aggregates or aggregates with said bituminous composition in a tank such as a kneader or a kneading drum,

- obtaining asphalt. Molecules of general formula II) or III) and their preparation

The subject of the invention also relates to the molecule of general formula (I) or (II) or their mixture

where Rci, R _C 2, R _A , R _B , X, X ', m and n meet the above definitions.

According to the invention, when the molecules (I) and (II) are taken individually, m and n are whole numbers between 1 and 25, when the molecules (I) and (II) are in mixture, one of the integers m and n can be equal to 0. In a mixture of molecules (I) and (II) according to the invention, at least one of the integers m and n is different from 0.

The preferential choices for the molecules of formulas (I) and (II) are the same as for the bituminous composition.

The molecules of general formula (I) or (II) can be synthesized by any method known to those skilled in the art.

In a particular embodiment, a diisocyanate and a diol and a precursor of the external chains (R _A , R _B ) can be brought into contact under conditions allowing an addition or polyaddition reaction between the reactants to form the molecule. formula (I) or (II) or a mixture thereof. For example, the external chain precursor can be a compound of formula R _A -OH, R _A -NH ₂ , R _B -OH, R _B -NH ₂ , OR a mixture of these compounds.

Advantageously, the synthesis is carried out in the presence of a catalyst. The catalyst can be chosen from tin octanoate, dibutyltin dilaurate (DBTDN), 1,4-diazabicyclo [2.2.2] octane (DABCO), trimethylamine ...

Advantageously, the synthesis is carried out in the presence of a solvent. The solvent can be chosen from organic solvents. Aprotic organic solvents are preferred. Mention may be made of tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, chloroform, etc. The synthesis can be carried out at a temperature between 20 and 200 ° C, more preferably between 20 and 100 ° C for a time which can range from 5 minutes to 24 hours, preferably from 2 hours to 8 hours.

The molar ratios between the reagents and the order of addition of said reagents are controlled to obtain the degree of repetition n or m of the central segment of the desired molecule of formula (I) or (II). The nature of the precursor of the external chain can also be controlled, as well as its functionalization in order to obtain the desired X and X ’function.

The different embodiments, variants, preferences and advantages described above for each of the objects of the invention apply to all of the objects of the invention and can be taken separately or in combination.

Analysis and methods

The following analyzes and methods are used for the characterization of the molecules of formula (I) or (II) and bituminous compositions according to the invention.

Fourier transform infrared spectrometry (FTIR): The infrared spectra are recorded using an Avatar FTIR 320 Is ^® 10 spectrometer, Nicolet company. The latter is equipped with an ATR ^® module (Attenuated Total Reflectance) for the analysis of samples in the solid state. When the spectrum of a solution is performed, the transmission mode is used as well as a KBr tank with 0.5 mm optical path.

Nuclear Magnetic Resonance (NMR): The 1H and ¹³ C spectra are acquired on the spectrometers, Bruker Avance 300 ^® (300 MHz) and Ultrashield 400 ^® (400 MHz) spectrometers. Internal calibrations are performed using the residual solvent signal.

Differential scanning calorimetry (DSC): The samples are analyzed in Tzero aluminum capsules. DSC measurements are carried out on a DSC Q2000 Auto ^® by TA Instruments apparatus, under nitrogen flow at 50 mL / min.

The invention is illustrated by the following examples given without limitation.

EXAMPLES

Material and methods

The rheological and mechanical characteristics of bitumens or bituminous compositions comprising the molecules of formula (I) or (II) to which reference is made in these examples are measured according to the methods indicated in Table 1. Table 1

Bitumen base

We choose a bitumen base of grade 70/100, denoted B ₀ , having a penetration P ₂₅ of 82 1/10 mm and a TBA of 46 ° C and commercially available from Total Marketing Services.

molecules

Ai: sebacic acid

A ₂ - Synthesis of the molecule A ₂ of formula (II):

8.3 ml of dimethylformamide (DMF) and then 0.165 ml (1.86 mmol, leq) are added to a 100 ml Schlenk flask containing a magnetic bar and equipped with a septum and an argon balloon. hexanediol and 0.60 mL (0.625 g, 3.72 mmol, 2eq) of hexamethylene diisocyanate. Finally, a few drops of tin octanoate (catalyst) are added. The mixture is brought to 70 ° C. for 1 h 10. Then 1.6 g (5.9 mmol, 1.5 eq) of octadecanol are added. Octadecanol was previously dried at 80 ° C under vacuum (10-3 mbar) for 48 hours. Agitation continues for 3 hours at 70 ° C. An infrared spectrum of the reaction medium makes it possible to control the disappearance of the peak linked to the isocyanate function (-2270 cm ¹ ). The product is concentrated in vacuo, precipitated in 80 ml of diethyl ether and filtered through a Buchner. A white solid is recovered and is dried under vacuum (1.6 g, 84%). The molecule A ₂ is characterized by NMR, DSC and LTIR-ATR. A mixture is mainly obtained comprising the molecule of formula (II) (25% by mass relative to all of the molecules resulting from the polyaddition reaction), in which: R _A = R _B = octadecyl; R _ci = R _c2 = hexyl; X = X '= urethane; n = 1.

1 H NMR (300 MHz, Chloroform-d): d 4.13 (t, 8H), 3.27 - 3.08 (t, 8H), 1.79 - 1.58 (m, 8H), 1.58 - 1.44 (m, 8H), 1.26 (s, 72H), 0.88 (t, 6H).

LTIR - ATR (cni ¹ ): 3317, 2917, 2850, 1683, 1538, 1261.

DSC (20 ° C / min, from -90 to 200 ° C): l 17 ° C (73 J / g), 136 ° C and 15 CU (44 J / g all). Example 1: Preparation of the additive bituminous compositions

The bituminous additive compositions are prepared by introducing the bitumen base B ₀ and the molecule in the proportions reported in Table 2 below into a reactor with stirring and at 170 ° C. The mixtures are stirred and heated at 170 ° C for about 30 minutes.

Table 2

Results

Table 3 below presents the physical characteristics of the bituminous compositions according to the invention (Ci and C ₂ ) and of the bituminous control compositions (To, Ti and

T ₂ ).

Table 3

^<d> : measurement uncertainty on the rheological data.

The compositions according to the invention and in particular the compositions Ci and C ₂ have properties superior to those of the bitumen alone To _, but also superior to those of the compositions Ti and T ₂ additivated with sebacic acid respectively at 3% and 5% by mass relative to the total mass of the bituminous composition. Note for the compositions according to the invention (Ci and C ₂ ) a decrease in the penetrability P _{25 in} particular compared to the bitumen alone T _o and an increase in the TBA compared to the bitumen alone T _o but also compared to the control compositions Ti and T ₂ . This translates into higher hardness and consistency for the compositions according to the invention.

In addition, it appears that the compositions according to the invention have viscosities at 180 ° C equivalent to those of pure bitumen T ₀ and that of compositions Ti and T ₂ .

The compositions according to the invention are therefore sufficiently fluid at the application temperatures, thus permitting good coating of the aggregates and placing of the coated materials on the road easier with the current technical means of the road profession.

Example 2: Preparation of bitumen breads

Bitumen breads Po, P _T2 and P _C2 are prepared according to the following method, respectively from the bitumen alone B ₀ , and from the control compositions T ₂ and from the composition according to the invention C ₂ . A mass of about 0.5 kg of bitumen is poured at 160 ° C into a rectangular steel mold covered with a polyethylene hot-melt film. The mold is then cooled to room temperature and then removed from the mold.

Creep test

A creep test is carried out beforehand. The test is carried out at a temperature of 70 ° C. and with a shear stress of 100 Pa with a shear rheometer of the MCR301® type from the Anton Paar brand. A 25 mm diameter plane-plane geometry module is used. The analysis is carried out as follows: the sample is crushed at 70 ° C between the two plates to a gap of 1.025 mm, the excess is leveled and the gap is adjusted to 1 mm (value used for analysis). A waiting time of 10 min allows the sample to be homogeneous in temperature and then the measurement begins. Figure 1 lists the results of the deformation as a function of time obtained for the different bitumen breads.

In FIG. 1, the deformation (without unit) is reported on the Y axis and the time in seconds is reported on the X axis. The curve in solid line represents that of the bread P ₀ ; the curve in dotted lines (-) represents that of bread P _T2 ; finally the curve with the circles (- O-) represents that of the bread P _C 2 ·

There is a marked improvement in the creep resistance of the bituminous breads Pc2 according to the invention compared to the bituminous breads Po which are not additivated, and even compared to the bituminous breads P _{| 2} additives with 5% by mass sebacic acid. Mechanical resistance test under compression stress

This test is carried out in order to evaluate the compressive strength of each bread Po, P T2 and P _C 2 when it is subjected to a load and at a temperature of 50 ° C.

The actual compressive strength test is carried out using a texture analyzer sold under the name LF Plus by the company LLOYD Instruments and equipped with a thermal enclosure. To do this, a metal and cylindrical box containing a mass of 60 g of bitumen bread is placed inside the thermal enclosure set at a temperature of 50 ° C. The piston of the texture analyzer is a cylinder with a diameter of 20 mm and a height of 60 mm. The cylindrical piston is initially placed in contact with the upper surface of the bitumen bar. Then, it moves vertically downwards, at a constant speed of 1 mm / min, over a calibrated distance of 10 mm so as to exert a compressive force on the upper surface of the bitumen bread. The texture analyzer measures the maximum compression force applied by the piston to the bitumen bread at 50 ° C. Measuring the maximum compressive force makes it possible to evaluate the capacity of the bitumen bread to resist deformation. Thus, the greater this force, the better the resistance to deformation of the bitumen bread. The results are listed in Table 4 below.

Table 4

The Pc2 breads according to the invention are particularly resistant to compression compared to the control bitumen breads Po based on bitumen alone and in Rc2 breads based on bitumen additivated with sebacic acid. The bread P _C 2 according to the invention is remarkable in that the maximum compression force is approximately 37 times greater than that applied to the control bitumen breads P _o and approximately 2 times greater than that applied to the bitumen breads Rc _å based on bitumen additivated with sebacic acid.

Thus, the bitumen breads according to the invention do not stick together and keep their shape and consistency even at high ambient temperature. Transport and / or storage are therefore optimized for the bitumen rolls according to the invention, with easier, safer handling and minimized bitumen losses.

Claims

1. Bituminous composition comprising at least one bitumen and at least one molecule of general formula (I) or (II) or a mixture thereof:

or :

- m and n are whole numbers between 0 and 25,

2. bituminous composition according to claim 1 in which Rci and Rc ₂ , identical or different, represent a hydrocarbon chain comprising from 2 to 18 carbon atoms, preferably from 2 to 12 carbon atoms, preferably from 2 to 10 atoms carbon, preferably from 2 to 8 carbon atoms, preferably from 4 to 8 carbon atoms.

3. bituminous composition according to claim 1 or 2 in which R _A and R _B, identical or different, represent a hydrocarbon chain comprising from 4 to 150 carbon atoms or an oligomer soluble in the bitumen chosen from polyolefins, polyetheroxides, polyacrylates, polymethacrylates, polysulfids, polystyrenics, polybutadienes, polyisobutenes, polyisoprenes, polyesters, polyamides, polysiloxanes, polyvinyl chlorides (PVC), polytetrafluoroethylenes (PTFE).

4. bituminous composition according to any one of claims 1 to 3 in which R _A and R _b , identical or different, represent a hydrocarbon chain chosen from octadecyl, oleyl, hexadecyl, tetradecyl, pentadecyl, heptadecyl, eicosyl, dodecyl, tridecyl, undecyl.

5. Bituminous composition according to any one of claims 1 to 4 in which X and X ′, identical or different, represent a urethane or urea function, preferably a urethane function.

6. bituminous composition according to any one of claims 1 to 5 comprising from 0.1 to 30% by mass of one or more molecules chosen from those of general formula (I) or (II), preferably from 0.5 to 20%, preferably from 1 to 10%, more preferably from 1.5 to 5%, even more preferably from 2 to 5%, by mass relative to the total mass of the bituminous composition.

7. Bituminous composition according to any one of claims 1 to 6 which is solid and in divided form at room temperature.

8. Bituminous composition according to claim 7 in the form of granules or breads.

9. Process for the preparation of a bituminous composition according to any one of claims 1 to 8, which comprises the following steps:

- the supply of a bituminous binder comprising at least one bitumen,

- bringing the molecule of general formula (I) or (II) into contact, at a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C, preferably between 110 and 180 ° C with the binder bituminous and then possibly - The shaping of the bituminous composition in divided form, and in particular in the form of breads or granules.

10. A method of transport and / or storage and / or handling of the bituminous composition according to any one of claims 1 to 8, or as prepared according to claim 9, said bituminous composition being transported and / or stored and / or handled at room temperature in divided and solid form, in particular in the form of breads or solid granules.

11. Molecule represented by the general formula (I) or (II) or their mixture:

in which

- m and n are whole numbers between 0 and 25,

when the molecules (I) and (II) are taken individually, m and n are whole numbers between 1 and 25,

when the molecules (I) and (II) are mixed, one of the integers m and n can be equal to 0.

12. Molecule according to claim 1 1 chosen from those corresponding to the following formulas: 13. Use of the bituminous compositions according to any one of claims 1 to 8 or prepared according to claim 9, in the fields of road applications, optionally in admixture with aggregates or aggregates of recycled bituminous mixes, in particular for making a coating surface, hot mix, cold mix, cold mix, severe emulsion, base coat, binder layer, bonding layer, wearing course, anti-omiant layer, draining mix, or asphalt, and in the fields of industrial applications, in particular for preparing a waterproofing coating, a membrane or an impregnation layer.