OA19552A - Bituminous composition for high modulus Mixes. - Google Patents

Abstract

The invention relates to a bituminous composition for making high modulus mixes. The invention also relates to a high modulus bituminous mix and the use of these mixes in the preparation of road pavements, in particular in the preparation of base layers or base layers for road pavements. The invention also relates to a method for transporting and / or storing and / or handling this bituminous composition which is solid at room temperature and in divided form.

Description

BITUMINOUS COMPOSITION FOR HIGH MODULE ASPHALT

Technical area

The present invention relates to the field of bitumens. More specifically, it relates to a bituminous composition making it possible to manufacture high modulus mixes.

The invention also relates to a high modulus bituminous mix and the use of these mixes in the preparation of road pavements, in particular in the preparation of base layers or base layers for road pavements.

The invention also relates to a process for transporting and / or storing and / or handling this bituminous composition which is solid at room temperature and in divided form.

State of the prior art

Much work has focused on improving the mechanical performance of materials used for pavement construction in order to increase their resistance to heavy road stresses.

More particularly, the use of so-called “hard” or “hard grade” bitumens is known, that is to say bitumens having a penetrability measured at 25 ° C according to standard EN 1426, of less than 35 1/10 mm. , for the production of high modulus asphalt due to the properties of hard bitumens intrinsically having a high modulus of rigidity for use on a roadway which has to withstand heavy road stresses.

In order to increase the hardness of a bitumen, it is known practice to mix a bitumen of a defined grade with a bitumen of a harder grade than the bitumen of a defined grade. However, this process has certain limits: for a significant increase in the hardness of a bitumen, bitumens of very low penetrability and in large quantities must be used, typically bitumens having a penetrability at 25 ° C ranging from 10 to 20 1/10 mm.

However, the supply of hard bitumens is becoming scarce due in particular to their very specific manufacturing process which only allows them to be obtained in limited quantities and requires the selection of specific crudes.

It is also known practice to add granules of hard bitumen or gilsonite to soft bitumens in order to increase their hardness. However, the availability of these additives is reduced and does not make it possible to obtain bitumens having satisfactory properties in terms of modulus.

It is also known to modulate the properties of a bitumen by applying an oxidizing treatment, such as blowing air, which increases the hardness of the bitumen. In fact, blown bitumens, also called oxidized bitumens, are obtained by blowing air with a bitumen base at temperatures ranging from 240 to 320 ° C.

EP 1 352 031 teaches a bitumen composition suitable for use in road construction, characterized in that the composition has a softening point of 50 to 75 ° C and comprises:

a) a blown bitumen having a penetrability at 25 ° C ranging from 10 to 50 1/10 mm, a Ball-Ring softening temperature (TBA) ranging from 70 to 120 ° C and a penetration index IP (European standard EN 12591 (1999), Appendix B) in the range 1.0 to 8.5, and

b) a solvent precipitated asphalt having a penetration at 25 ° C ranging from 0 to 40 1/10 mm.

The use of blown bitumens alone does not allow the manufacture of high modulus asphalt.

FR 2 153 751 teaches: on the one hand, subjecting the residue of the vacuum distillation of a crude oil to an oxidation treatment. On the other hand, to fractionate the residue from the vacuum distillation of a crude oil, identical or not to the previous one, into deasphalted residue and deasphalting bitumen. One part by weight of the oxidized residue and 0.5 to 2 parts by weight of the deasphalting bitumen thus obtained are mixed, and finally a suitable plasticizer is added to this mixture, so as to adjust the hardness of the bituminous binder to the desired value. . However, this method involves several processing and recomposition operations which must be adapted according to the original stock.

It is also known to modulate the properties of a bitumen by mixing with other components.

WO 2010/043945 describes a high modulus bituminous mix based on pavement material recycling mills comprising residual bituminous binder, new aggregates and bituminous binder input.

However, this composition is obtained following several processing and recomposition operations. Such operations are difficult to implement in certain geographic areas where facilities for recycling pavement materials are rare or even non-existent.

WO 2010/086561 describes a bituminous mix or bituminous concrete with a high modulus based on a bituminous binder comprising at least one bitumen and at least one natural or synthetic resin and aggregates.

US 2004/0094454 describes petroleum binders comprising a pitch of petroleum origin and a fraction of bitumen obtained from a crude oil of petroleum origin.

KR 2004 0001331 describes bituminous compositions with improved crack resistance and low temperature flow resistance. These bituminous compositions comprise a bitumen base and a pitch of petroleum origin.

However, due to the difficulty linked to the geographical availability and / or to the supply of additives such as resin, this type of composition cannot be implemented at competitive costs in all distribution areas where such compositions are needed.

Therefore, there is a need to provide a bituminous composition exhibiting, inter alia, a high modulus meeting the drawbacks of the prior art mentioned above. More particularly, there is a need to provide, in industrial quantities, a bituminous composition exhibiting a high modulus, satisfactory for its use in the road sector.

In addition, it was highlighted the scarcity of hard bitumens with a high modulus in certain geographical areas, such as for example in Africa and the Middle East, because such bitumens are difficult to handle because they need to be heated. at high temperature. Therefore, for use in these geographical areas, they must be transported, which can only be done in molten, hot form, which poses ecological, economic and logistical problems.

Typically, bitumen is stored and transported hot, in bulk, in tankers or by ships at high temperatures in the range of 120 ° C to 160 ° C. However, the storage and transport of hot bitumen has certain drawbacks. On the one hand, the transport of hot bitumen in liquid form is considered dangerous and it is very regulated from a regulatory point of view. This mode of transport does not present any particular difficulties when the equipment and transport 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 too long journey. The bitumen delivery distances are therefore limited. On the other hand, keeping bitumen at high temperatures in tanks or tankers consumes energy. In addition, maintaining the bitumen at high temperatures for a long time can affect the properties of the bitumen and thus change the final performance of the asphalt.

To overcome the problems of transporting and storing hot bitumen, packaging allowing the transport and storage of bitumens at room temperature have been developed. This mode of transporting bitumen in ambient temperature packaging represents only a small fraction of the quantities transported worldwide, but it corresponds to very real needs for geographic regions that are difficult and expensive to access by traditional means of transport.

As an example of packaging for cold transport currently used, we can cite the packaging of bitumen at room temperature in metal drums. This method is increasingly questionable from an environmental point of view because the bitumen stored in the drums must be heated before its use as a road binder. However, this operation is difficult to implement for this type of packaging and the drums constitute waste after use. On the other hand, the storage of bitumen at room temperature in drums leads to losses because the bitumen is very viscous and part of the product remains on the walls of the drum during transfer into the tanks of the asphalt production units. Handling and transporting bituminous products in these drums can be difficult and dangerous if specialized drum handling equipment is not available from carriers or where the bitumen is used.

Other examples of packaging include bitumens in the form of granules transported and / or stored in bags, often used in places where the ambient temperature is high. These granules have the advantage of being easy to handle. US 3,026,568 describes bitumen granules covered with a powdery material, such as limestone powder. However, this type of granular bitumen does not prevent the bitumen from creeping, especially at high ambient temperature.

As other packaging examples, mention may be made of bituminous compositions comprising a chemical additive in the form of blocks or granules described in WO 2016/016318 and in WO 2016/016320 making it possible to transport and / or store and / or handle the product. bitumen at room temperature

However, depending on the grades of bitumen used, either the modulus properties of some of these compositions are not sufficiently satisfactory for use on a roadway having to withstand very strong road stresses, or it becomes difficult to obtain in industrial quantities of hard grade bitumens making it possible to obtain high modulus mixes.

There is also a need to provide a bituminous composition exhibiting, inter alia, a high modulus, the transport and / or storage and / or handling of which is simplified regardless of the geographical area of its implementation compared to the bituminous compositions described in l. prior art.

The Applicant has observed that the addition of a particular pitch in a bitumen made it possible to obtain, in industrial quantities, hard bitumens having very satisfactory modulus properties making it possible to satisfactorily solve the problems mentioned above.

More particularly, the Applicant has demonstrated that such compositions exhibiting very satisfactory modulus properties could be readily available in industrial quantities and in a form allowing it to be transported, stored and handled at room temperature, even at a temperature. high ambient. In this case, the proposed bituminous composition is in divided and solid form at room temperature so that it satisfactorily solves the problems mentioned above.

Summary of the invention

The invention relates to a bituminous composition characterized in that the composition comprises:

a) at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TB A is measured according to standard EN 1427, and

b) at least one bitumen base.

According to a preferred embodiment, the pitch is an oxidized pitch.

According to a preferred embodiment, the pitch is present in an amount ranging from 2 to 30% by mass relative to the total mass of the composition.

According to a preferred embodiment, the bituminous composition according to the invention is in cold solid form and in divided form.

According to a more preferred embodiment, the bituminous composition is solid when cold and in divided form, and further comprises at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures.

According to a preferred embodiment, the bituminous composition comprises from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.8% by mass, and even more preferably from 0.5% to 2.5% by mass of said chemical additive relative to the total mass of the bitumen base.

According to a preferred embodiment, the chemical additive is an organic compound which has a molar mass by mass of less than or equal to 2000 gmol ' ¹ , preferably a molar mass of less than or equal to 1000 gmol' ¹ .

According to a preferred embodiment, the bituminous composition is in the form of a bar or of granules.

The invention also relates to a process for manufacturing a bituminous composition, this process comprising the following steps:

- Heating of the bitumen base b) to a temperature ranging from 140 to 180 ° C,

- Introduction of pitch a) into the bitumen base b),

- Stirring the mixture at a temperature ranging from 140 to 180 ° C until a homogeneous mixture is obtained.

According to a preferred embodiment of the process, the pitch is introduced in the form of granules.

The invention also relates to a kit capable of being used for the manufacture of a bituminous composition as defined above, this kit comprising at least:

- a solid bitumen base cold and in divided form,

- a capsule comprising at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427 in the form of a granule.

According to a preferred embodiment of the kit, the solid bitumen base when cold and in divided form is in the form of a bar.

According to a preferred embodiment of the kit, the cold solid bitumen base in divided form comprises on one of its faces a cavity making it possible to accommodate all or part of the capsule.

According to a preferred embodiment of the kit, the capsule is housed in whole or in part in said cavity in a removable manner.

A subject of the invention is also a process for preparing a solid bituminous composition under cold conditions and in divided form comprising at least one bituminous composition and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures. , the method comprising:

- the mixture of at least one bituminous composition and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, to form a bituminous composition with additives,

- shaping of the bituminous composition with additives in the form of a bar or granules.

A subject of the invention is also a method for transporting and / or storing and / or handling the solid bituminous composition in cold condition and in divided form, said bituminous composition being transported and / or stored and / or handled in the form of bars. or granules of bituminous composition which are solid at room temperature.

The invention also relates to the use of the bituminous composition described above and in detail below for the manufacture of bituminous mixes or bituminous concretes.

The subject of the invention is also bituminous mixes or concretes comprising the bituminous composition described above and in detail below, and aggregates.

The invention also relates to a process for manufacturing bituminous mixes or bituminous concretes comprising at least one bituminous composition and aggregates, the bituminous composition being chosen from solid bituminous compositions in cold form and in divided form, this method comprising at least the stages of:

- heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C,

- mixing the aggregates with the solid bituminous composition cold and in divided form in a tank such as a mixer or a mixer drum,

- obtaining of asphalt.

According to a preferred embodiment, this process does not include a step of heating the solid bituminous composition cold and in divided form before it is mixed with the aggregates.

The invention further relates to the use of a pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C. , it being understood that the penetrability is measured according to the standard EN 1426 and that the TBA is measured according to the standard EN 1427 to increase the modulus of a bituminous composition.

detailed description

The objectives that the applicant has set have been achieved thanks to the development of bitumen compositions comprising a particular pitch making it possible to achieve satisfactory properties for bituminous compositions intended to be used for road applications, in particular a pitch. improved modulus compared to bituminous compositions known from the prior art.

They have also been achieved thanks to the use of these bituminous compositions in a divided and solid form at room temperature, giving said compositions improved properties, in particular of modulus, thus making it possible to transport them and / or to store and / or to store them. to handle more easily compared to the bitumen compositions known from the prior art.

A first object of the invention relates to a bituminous composition comprising:

a) at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427, and

b) at least one bitumen base.

The invention also relates to a process for manufacturing a bitumen composition as described above and in more detail below, this process comprising the following steps:

- Heating of the bitumen base b) to a temperature ranging from 140 to 180 ° C,

- Introduction of pitch a) into the bitumen base b),

- Stirring the mixture at a temperature ranging from 140 to 180 ° C until a homogeneous mixture is obtained.

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

By "bitumen" is meant any bituminous composition consisting of one or more bitumen bases, said composition being intended for road application.

The term “pitch” is understood to mean, according to the present invention, a residue from the distillation of petroleum.

According to the invention, the bitumen base is chemically different from the pitch used. Therefore, the bitumen base and the pitch cannot be used as a replacement for the other because their chemical characteristics are different.

By "penetrability" is meant here the so-called "needle penetrability" measurement which is carried out by means of a standardized test NF EN 1426 at 25 ° C (P25). This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). The needle penetrability, measured at 25 ° C, according to the standardized test NF EN 1426, represents the measurement of the penetration in a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100g. Standard NF EN 1426 replaces approved standard NF T 66-004 of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated November 20, 1999).

The term “softening point” is understood to mean the so-called “softening point” measurement which is carried out by means of a standardized test NF EN 1427. The ring ball softening point corresponds to the temperature at which a steel ball of standard diameter, after having passed through the material to be tested (glued in a ring), reaches the bottom of a standardized vessel filled with a liquid which is gradually heated, and in which the device has been immersed.

The term “modulus” is understood to mean the measurement defining the ratio of the amplitude of the stress to the amplitude of the deformation in harmonic sinusoidal oscillation which is carried out by means of a standardized test NF EN 14770. The modulus of the bituminous composition also called complex modulus or modulus of rigidity of the bituminous composition is determined by means of a dynamic shear rheometer. To do this, a series of sinusoidal deformations of defined frequencies are applied to the sample maintained at a defined temperature. According to standard NF EN 14770, the complex modulus of the bituminous composition is determined for a sinusoidal deformation of frequency between 0.1 and 10 Hz at a temperature ranging from 5 to 85 ° C. In the invention, the complex modulus of the bituminous composition was determined for a sinusoidal deformation of frequency 10 Hz at a temperature of 15 ° C and also at a temperature of 60 ° C. To determine the modulus of the bituminous composition, the bituminous composition is placed between two parallel planes, one fixed, the other mobile. The higher amount imposes the shear strain, the resulting strain is raised.

By “modulus of mixes” is meant the measurement of the complex modulus of rigidity of bituminous mixes according to standard NF EN 13108-1. In the invention, the complex modulus of asphalt mixes was determined for a sinusoidal deformation of frequency 10 Hz at a temperature of 15 ° C.

According to one embodiment of the invention, the pitch is in the form of granules before it is introduced into the heated bitumen base. Such an embodiment facilitates the handling of the components and the implementation of the method.

According to one embodiment of the invention, the pitch is a blown pitch. For the purposes of the invention, the terms "blown pitch" and "oxidized pitch" will be used independently of one another.

According to one embodiment of the invention, the bituminous composition comprises from 2 to 30% by mass of pitch relative to the total mass of the composition, preferably from 3 to 20% by mass of pitch relative to the total mass of the composition.

The expression "consists essentially of" or "consists essentially of" followed by one or more characteristics, means that may be included in the process or material of the invention, in addition to the components or steps explicitly listed, components or steps which do not significantly modify the properties and characteristics of the invention.

Pitch

According to the French dictionary, "pitch" is understood to mean a residue from the distillation of petroleum, petroleum, coal, wood or other organic molecules.

The invention relates here to residues from the distillation of petroleum, also called "petroleum pitch".

For the purposes of the invention, the terms "pitch", "petroleum pitch" and "deasphalting pitch" will be used independently of one another.

Pitches can be obtained by conventional refinery manufacturing processes. The manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation. First, the crude oil is subjected to distillation at atmospheric pressure, which results in a gas phase, different distillates and an atmospheric distillate residue. Then, the residue from the atmospheric distillation is itself subjected to a distillation under reduced pressure, called vacuum distillation, which separates a heavy gas oil, various still cuts and a residue of vacuum distillation. This vacuum distillation residue contains "petroleum pitch" in varying concentration.

It is possible to obtain the "petroleum pitch" according to two processes: ^1st process:

The vacuum distillation residue is subjected to a dealphalting operation by the addition of a suitable solvent, such as propane, which thus makes it possible to precipitate the pitch and separate it from light fractions such as deasphalted oil.

2 ^nd method:

The vacuum distillation residue is subjected to extraction with solvent, and more precisely with furfuraldehyde. This heterocyclic aldehyde has the particularity of selectively solubilizing aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the "petroleum pitch".

According to one embodiment, the pitch is an oxidized pitch.

Preferably, the oxidized pitch according to the invention is obtained by oxidation of a mixture comprising pitch and a diluent, such as a light gasoline, also called a “flux” subjected to an oxidation operation in a blowing tower in presence of a catalyst, at a fixed temperature and at a given pressure.

For example, oxidized pitches can be made in a blowing unit, by passing a flow of air and / or oxygen through a starting pitch. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the oxidation is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long times, typically between 30 minutes and 2 hours, continuously or in batches. The duration and temperature of the oxidation are adjusted according to the properties targeted for the oxidized pitch and according to the quality of the starting pitch.

The mechanical qualities of pitches are generally assessed by determining a series of mechanical characteristics by standardized tests, the most widely used of which are needle penetrability expressed in 1/10 mm and the softening point determined by the ball and ring test. , also called ball and ring softening temperature (TBA).

According to one embodiment of the invention, the pitch exhibits needle penetrability at 25 ° C from 0 to 20 1/10 mm, preferably from 0 to 15 1/10 mm, more preferably from 0 to 10 1 / 10 mm, it being understood that the penetrability is measured according to standard EN 1426.

According to one embodiment of the invention, the pitch has a softening point of between 115 ° C and 175 ° C. Among examples of pitches used in the invention, there are pitches having respectively a softening point of between 115 ° C and 125 ° C, between 135 and 145 ° C or also between 165 and 175 ° C.

The addition of a pitch with the mechanical characteristics presented above in a bituminous composition makes it possible to improve the modulus properties of said bituminous composition and also to improve the modulus properties of asphalt mixes. In addition, the addition of the pitch according to the invention in a bituminous composition makes it possible to reduce the penetrability and to increase the ball-ring softening temperature of said bituminous composition while maintaining the viscosity of said bituminous composition relative to a composition. bituminous without pitch.

According to one embodiment of the invention, the pitch is cold solid and in divided form. This shape facilitates the handling of the pitch for its use in the manufacture of the bituminous composition.

The term “solid cold pitch and in divided form” is understood to mean a pitch that is solid at room temperature which is packaged in a divided form, that is to say in the form of units which are distinct from each other, for example granules.

According to one embodiment of the invention, the cold solid pitch is in the form of granules.

The pitch 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. More specifically, the pitch granules according to the invention preferably have a cylindrical or spherical shape.

According to one embodiment of the invention, the size of the pitch granules is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably 2 to 30 mm. For example, the use of a die makes it possible to control the production of granules of a chosen size. A sieving makes it possible to select granules according to their size.

To allow the formation of pitch granules which do not adhere to each other and resist compression during storage, it may be advantageous to coat all or part of the surface of the pitch granules with an anti-caking agent.

The pitch, in the form of granules optionally covered with an anti-caking compound, is easily handled after a period of transport and / or prolonged storage.

Process for manufacturing a bituminous composition:

A subject of the invention is also a process for manufacturing a bituminous composition comprising at least one pitch a) and at least one bitumen base b), as defined above.

This method comprising at least the steps of:

- Heating of the bitumen base b) to a temperature ranging from 140 to 180 ° C,

- Introduction of pitch a) into the bitumen base b),

- Stirring the mixture at a temperature ranging from 140 to 180 ° C until a homogeneous mixture is obtained.

It has surprisingly been observed that the pitch mixes perfectly with the bitumen base.

Advantageously, the pitch does not need to be heated, before being added to the bitumen base.

Although the pitch usually has a melting point above 220 ° C., it dissolves in bitumens at the usual temperatures for preparing bituminous compositions. On the other hand, hard bitumens must be heated beforehand in order to be incorporated into a bituminous composition.

The process for manufacturing the bituminous composition is easy to implement and does not require hot transport over long distances the pitch intended to improve the properties of the bitumen base, unlike the “hard” grade bitumen bases used in the process. prior art.

Advantageously, a bitumen base produced in the application zone can be used and its properties improved by the addition of pitch.

Cold solid bituminous composition in divided form

The bituminous composition according to the invention can be provided in cold solid form and in divided form.

By “cold solid bitumen” is meant a bitumen exhibiting a solid appearance at room temperature regardless of the transport and / or storage conditions. More precisely, by solid bitumen at room temperature is meant a bitumen which retains its solid appearance throughout transport and / or storage at room temperature, that is to say a bitumen which does not flow at room temperature under its own weight and moreover, which does not creep when subjected to pressure forces resulting from transport and / or storage conditions.

According to one embodiment, the cold solid bituminous composition in divided form comprises:

a) at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427,

b) at least one bitumen base, and

c) at least one chemical additive.

For the purposes of the invention, the solid bituminous composition when cold and in divided form is also called "bituminous composition with additives".

According to one embodiment, the bituminous composition according to the invention, which is cold solid and in divided form, comprises at least one chemical additive chosen from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof.

In particular, the solid bituminous composition and in divided form comprises at least one chemical additive in an amount suitable so that its penetrability is preferably 5 to 70 1 / 10mm, preferably 10 to 60 1 / 10mm, it being understood that the penetrability is measured at 25 ° C according to standard EN 1426.

Another object relates to the use of a pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to the standard EN 1426 and that the TBA is measured according to the standard EN 1427 to increase the modulus of a bituminous composition.

Bitumen base

For the purposes of the invention, the terms "bitumen" and "road bitumen" are used equivalently and independently of each other. By "bitumen" or "road bitumen" is meant any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives and / or one or more elastomers, said compositions being intended for road application.

Among the bitumen bases that can be used according to the invention, there may be mentioned first of all bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or tar sands and bitumens from the refining of crude oil. . The bitumen bases according to the invention are advantageously chosen from bitumen bases obtained from the refining of crude oil. The bitumen bases can be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes.

Bitumen bases can be obtained by conventional processes for manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumen bases can optionally be vis-reduced and / or deasphalted and / or air-rectified. It is common practice to perform vacuum distillation of atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feed supplying 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 practice to inject air into a feed usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This process makes it possible to obtain a blown base, or semi-blown or oxidized or air-rectified or partially air-rectified.

The different bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise. The bitumen base can also be a recycling bitumen base. Bitumen bases can be hard grade or soft grade bitumen bases.

According to the invention, for the conventional methods of manufacturing bitumen bases, the operation is carried out at manufacturing temperatures of between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, more preferably between 140 ° C and 170 ° C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The term “production temperature” is understood to mean the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and duration of the heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594.

Preferably, the bitumen base used in the invention has a needle penetrability measured at 25 ° C according to standard EN 1426 from 30 to 330 1/10 mm, preferably from 30 to 220 1/10 mm.

According to one embodiment of the invention, the bitumen base can also comprise at least one known elastomer for bitumen such as the copolymers SB (block copolymer of styrene and butadiene), SBS (styrene-butadiene-styrene block copolymer) , SIS (styrene-isoprenestyrene), SBS * (styrene-butadiene-styrene star block copolymer), SBR (styrene-butadiene-rubber), EPDM (modified ethylene propylene diene). These elastomers can also be crosslinked according to any known process, for example with sulfur. Mention may also be made of elastomers made from styrene monomers and butadiene monomers allowing crosslinking without a crosslinking agent, as described in documents WO2007 / 058994, WO2008 / 137394 and by the applicant in patent application WO11 / 013073.

Preferably, the bituminous composition comprises from 70% to 99.9% by mass of bitumen base, relative to the total mass of the bituminous composition, preferably from 75% to 99.5%, even more preferably from 80% to 99%.

According to one embodiment of the invention, the bituminous composition comprises from 0.5% to 15% by mass, preferably from 1% to 15% by mass, more preferably from 2% to 12% by mass of elastomer per relative to the total mass of the bituminous composition.

Additive

The chemical additive is chosen from: an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof.

In one embodiment of the invention, the chemical additive is an organic compound. Advantageously, the organic compound has a molar mass of less than or equal to 2000 gmol ′ ¹ , preferably a molar mass of less than or equal to 1000 gmol ′ ¹ .

In this first embodiment, according to a first variant, the organic compound is a compound of general formula (I):

Arl-R-Ar2 (I), in which:

• Arl and Ar2 represent, independently of one another, a benzene ring or a system of condensed aromatic rings of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and • R represents an optionally substituted divalent radical, of which the main chain comprises from 6 to 20 carbon atoms and at least one group chosen from the amide, ester, hydrazide, urea, carbamate and anhydride functions.

Preferably, Arl and / or Ar2 are substituted by at least one alkyl group of 1 to 10 carbon atoms, advantageously in one or more positions ortho with respect to the hydroxyl group (s), more preferably Arl and Ar2 are 3,5-dialkyl-4-hydroxyphenyl groups, advantageously 3,5-di-ter / -butyl-4-hydroxyphenyl groups.

Preferably, R is in the para position with respect to a hydroxyl group of Ar1 and / or Ar2.

Advantageously, the compound of formula (I) is 2 ’, 3-bis [(3- [3, 5-di-tert-butyl-4hydroxyphenyl] propionyl)] propionohydrazide.

According to a second variant of this first embodiment, the organic compound is a compound of general formula (II):

R- (NH) _n CONH- (X) _m -NHCO (NH) _n -R '(II), in which,

- the groups R and R ', identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles;

- the group X contains a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles;

- n and m are integers with a value of 0 or 1 independently of each other.

According to this variant, when the integer m has a value of 0, then the R- (NH) _n CONH and NHCO (NH) _n -R 'groups are covalently linked via a CONH-NHCO hydrazide bond. The R group, or the R ′ group, then comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms, an aliphatic ring of 3 to 8 atoms, an aliphatic, partially aromatic or entirely condensed polycyclic system. aromatic, each ring comprising 5 or 6 atoms.

Still according to this variant, when the integer m has a value of 1, then the group R, the group R 'and / or the group X, comprises at least one group chosen from: a hydrocarbon chain of at least 4 carbon atoms , an aliphatic ring of 3 to 8 atoms, an aliphatic, partially aromatic or fully aromatic condensed polycyclic system, each ring comprising 5 or 6 atoms.

Preferably, the group R and / or R 'comprises an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular, chosen from the groups C4H9, C5H11, C9H19, CnH ₂₃ , C12H25, C17H35, CigH ₃ 7, C21H43, C22H45 .

Preferably, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms. Preferably, the X group is chosen from C2H4, 63¾ groups.

Preferably, the X group can also be a cyclohexyl group or a phenyl group, the R- (NH) _n CONH- and NHCO (NH) _n -R'- radicals can then be in the ortho, meta or para position. Furthermore, the R- (NH) _n CONH- and NHCO (NH) _n -R'- radicals can be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring can be substituted by groups other than the two main groups R (NH) _n CONH- and -NHCO (NII) _n -R '.

Preferably, the X group comprises two rings of 6 carbon atoms linked by a CH ₂ group, these rings being aliphatic or aromatic. In this case, the group X is a group comprising two aliphatic rings linked by an _{optionally substituted CH 2} group, for example:

Advantageously, according to this variant, the organic compound is a compound of general formula (II) chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCOC5H11, C9Hi9-CONH-NHCO-C9H ₁₉ , CiiH ₂ 3-CONH-NHCO- ChH ₂₃ , C ₁₇ H ₃₅ -CONH-NHCO

C17H35, or C21H43-CONH-NHCO-C21H43; diamides such as N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35; and ureid derivatives such as 4,4'bis (dodecylaminocarbonylamino) diphenylmethane of formula C12H25-NHCONH-C6H4-CH2C ₆ H4-NHCONH-C12H ₂₅ .

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition n = 0.

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.

Preferably, the compound of general formula (II) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.

Preferably, according to a first variant, the compound of general formula (II) is chosen from those of formula (IIA):

R-CONH- (X) _m -NHCO-R '(IIA) in which R, R', m and X have the same definition as above.

Preferably, in formula (IIA) when m = 1, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms, advantageously X represents a linear, saturated hydrocarbon chain comprising from 1 to 12 carbon atoms , even better from 1 to 4 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C3H6.

Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the sum of the numbers of the carbon atoms of R, X and R 'is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.

Preferably, the compound of general formula (IIA) is chosen from those which satisfy the condition: the number of carbon atoms of at least one of R and R 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.

More preferably, according to this variant, the compound of general formula (IIA) is chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCO-C5H11, C9H19-CONHNHCO-C9H19, C11H23-CONH-NHCO-C11H23, C17H35-CONH -NHCO-C17H35, or C21H43-CONHNHCO-C21H43; diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23CONH-CH2-CH2-NHCO-C11H23, N, N'-ethylenedi (myristylamide) of formula C13H27-CONHCH2-CH2-NHCO-C13H27, N , N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH219552

NHCO-C15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCOC17H35; mono amides such as laurylamide of formula C11H23-CONH2, myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35-CONH2.

Even more advantageously, the compound of general formula (IIA) is N, N'ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35.

Preferably, according to a second variant, the compound of general formula (II) is chosen from those of formula (IIB):

R-CONH-R ’(IIB) where R and R’ have the same definition as above.

Advantageously, according to this variant, the sum of the numbers of the carbon atoms of R and R ′ is greater than or equal to 10, advantageously greater than or equal to 14, preferably greater than or equal to 18.

Even more advantageously, according to this variant, the number of carbon atoms of R is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14, and R ′ = H.

Advantageously, the compound of general formula (II) is chosen from hydrazide derivatives such as the compounds C5H11-CONH-NHCO-C5H11, C9H19-CONH-NHCO-C9H19, CHH23-CONH-NHCO-C11H23, C ₁₇ H35-CONH- NHCO-C1 ₇ H35, or C21H43-CONH-NHCOC21H43; diamides such as N, N'-ethylenedi (laurylamide) of formula C11H23-CONH-CH2CH2-NHCO-C11H23, N, N'-ethylenedi (myristylamide) of formula C13H27-CONH-CH2-CH2NHCO-C13H27, N , N'-ethylenedi (palmitamide) of formula C15H31-CONH-CH2-CH2-NHCOC15H31, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35; mono amides such as laurylamide of formula CHH23-CONH2, myristylamide of formula C13H27-CONH2, palmitamide of formula C15H31-CONH2, stearamide of formula C17H35CONH2.

Even more advantageously, the compound of general formula (II) is N, N'ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35.

Preferably, when the chemical additive is chosen from organic compounds of formula (II), it is used in combination with at least one other chemical additive chosen from organic compounds of formula (I), (III), (V) , (VI) and (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV).

According to a third variant of this embodiment, the organic compound is a compound of formula (III):

(R-NHCO) _X -Z- (NHCO-R ') _y (III), in which,

- R and R ’, identical or different, contain a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles,

- Z represents a tri-functionalized group chosen from the following groups:

- x and y are different integers of value varying from 0 to 3 and such that x + y = 3.

Preferably, when x is equal to 0 and Z represents Z ₂ , the compound of formula (III) is N2, N4, N6-tridecylmelamine having the following formula with R 'representing the group C9H19:

Other preferred compounds corresponding to formula (III) are such that x is equal to 0, Z represents Z ₂ and R 'represents a saturated, linear hydrocarbon chain, from 1 to 22 carbon atoms, preferably from 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.

Other preferred compounds corresponding to formula (III) are such that: y is equal to 0 and Z represents Z], the compounds then have the formula:

Ο ΗΝ ^

R with R chosen from the following groups, taken alone or as mixtures:

Other preferred compounds corresponding to formula (III) are such that: y is equal to 0, Z represents Zi and R represents a saturated, linear hydrocarbon chain, from 1 to 22 carbon atoms, preferably from 8 to 12 atoms. of carbon.

According to a fourth variant of this embodiment, the organic compound is a reaction product of at least one C3-C12 polyol and at least one C2-C12 aldehyde. Among the 10 polyols which can be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol.

Advantageously, according to this variant, the organic compound is a compound which comprises at least one function of general formula (IV):

with:

x is an integer,

- R is chosen from an alkyl, alkenyl, aryl or aralkyl radical in Cl-Cll, optionally substituted by one or more halogen atoms, one or more alkoxy groups in C1-C6

The organic compound is advantageously a derivative of sorbitol. By “sorbitol derivative” is meant any reaction product obtained from sorbitol. In particular, any reaction product obtained by reacting an aldehyde with D-sorbitol. By this condensation reaction, sorbitol acetals, which are sorbitol derivatives, are obtained. 1,3: 2,4-Di-Obenzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:

The sorbitol derivatives can thus be all the condensation products of aldehydes, in particular of aromatic aldehydes with sorbitol. We will then obtain sorbitol derivatives of general formula:

OH

HO - where Ari and Ar2 are optionally substituted aromatic rings.

Among the sorbitol derivatives, other than 1,3: 2,4-Di-O-benzylidene-D-sorbitol, there can be found, for example, 1,3: 2,4: 5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono-O-benzylidene-D-sorbitol, l, 3: 2,4-bis (p-methylbenzylidene) sorbitol, l, 3: 2,4-bis (3,4- dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (p-ethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-propylbenzylidene) sorbitol, l, 3: 2,4-bis (pbutylbenzylidene) sorbitol, l, 3: 2,4-bis (p-ethoxylbenzylidene) sorbitol, l, 3: 2,4-bis (pchlorobenzylidene) sorbitol, l, 3: 2,4-bis (p-bromobenzylidene) sorbitol, 1,3: 2,4-Di-O methylbenzylidene-D-sorbitol, 1,3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, 1,3: 2,4-Di-O- (4methylbenzylidene) -D-sorbitol , 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol. Preferably, according to this variant, the organic compound is 1,3: 2,4-Di-O-benzylidene-Dsorbitol.

According to a fifth variant of this embodiment, the organic compound is a compound of general formula (V):

R ”- (COOH) _Z (V), in which R” represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms, preferably from 4 to 54 carbon atoms, more preferably from 4 to 36 carbon atoms and z is an integer ranging from 2 to 4.

Preferably, the group R ”is a saturated linear chain of formula C _W H2 _W with w an integer varying from 4 to 22, preferably from 4 to 12.

According to this variant of the invention, the organic compounds corresponding to formula (V) can be diacids (z = 2), triacids (z = 3) or tetracids (z = 4). The preferred organic compounds according to this variant are diacids with z = 2.

Preferably, according to this variant, the diacids have the general formula HOOC-C _W H2 _W -COOH with w an integer varying from 4 to 22, preferably from 4 to 12 and where z = 2 and

R = C _w H _2w .

Advantageously, according to this variant, the organic compound is a diacid chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

More preferably, the organic compound is sebacic acid or 1,10-decanedioic acid with w = 8.

The diacids can also be diacid dimers of unsaturated fatty acid (s), that is to say dimers formed from at least one unsaturated fatty acid, for example from a single fatty acid. unsaturated or from two different unsaturated fatty acids. The diacid dimers of unsaturated fatty acid (s) are conventionally obtained by intermolecular dimerization reaction of at least one unsaturated fatty acid (Diels Aider reaction, for example).

Preferably, a single type of unsaturated fatty acid is dimerized. They are derived in particular from the dimerization of an unsaturated fatty acid, in particular Cg to C34, particularly C12 to C22, particularly IC6 -C ₂ o, and more particularly Cig. A preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or totally hydrogenated.

Another preferred fatty acid dimer has the formula HOOC- (CH2) 7-CH = CH- (CH2) 7-COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. Likewise, one can find fatty acid triacids and fatty acid tetracids, obtained respectively by trimerization and tetramerization of at least one fatty acid.

According to a sixth variant of this embodiment, the organic compound is a compound of general formula (VI):

^ (ch ₂ ) _p ^ y ^Y o

in which,

- the groups Y and Y 'represent, independently of one another, an atom or group chosen from: H, - (CH2) q-CH3, - (CH2) q-NH2, - (CH2) q-OH, - (CH2) q-COOH or ^ (CH ₂ ) _p ^

- (CH ₂ ) _q -NH- (CH ₂ ) _q -N. .NOT.

ΙΊ ^H

O with q an integer varying from 2 to 18, preferably from 2 to 10, preferably from 2 to 4 and p an integer greater than or equal to 2, preferably having a value of 2 or 3.

Among the preferred organic compounds corresponding to formula (VI), mention may be made of the following compounds:

Preferably, according to this variant, the organic compound of general formula (VI) is:

According to a seventh variant of this embodiment, the organic compound is a compound of general formula (VII):

R-NH-CO-CO-NH-R '(VII) in which, R and R', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising heteroatoms, rings and / or heterocycles.

According to another embodiment of the invention, the chemical additive is a paraffin. Paraffins have chain lengths of 30 to 120 carbon atoms (C30 to C120). The paraffins are advantageously chosen from polyalkylenes.

Preferably, polymethylene paraffins and polyethylene paraffins will be used according to the invention. These paraffins can be of petroleum origin or come from the chemical industry.

Advantageously, the paraffins used are synthetic paraffins resulting from the conversion of biomass and / or natural gas.

Preferably, these paraffins contain a large proportion of so-called “normal” paraffins, that is to say straight-chain, unbranched linear paraffins (saturated hydrocarbons). Thus, paraffins can include 50 to 100% normal paraffins and 0 to 50% isoparaffins and / or branched paraffins. More preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins and / or branched paraffins. Advantageously, the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins. Even more preferably, the paraffins comprise 85-95% normal paraffins and 5-15% isoparaffins.

Preferably, the paraffins are polymethylene paraffins. More particularly, the paraffins are synthetic polymethylene paraffins, for example paraffins obtained from the conversion of synthesis gas by the Fischer-Tropsch process. In the FischerTropsch process, paraffins are obtained by reacting hydrogen with carbon monoxide over a metal catalyst. Fischer-Tropsch synthesis methods are described, for example, in publications EP 1 432 778, EP 1 328 607 or EP 0 199 475.

According to another embodiment of the invention, the chemical additive is a polyphosphoric acid. The polyphosphoric acids (PPA) which can be used in the invention are described in WO 97/14753. These are compounds of the molecular formula PqHrOs in which q, r and s are positive numbers such as:

q> 2 and in particular q ranges from 3 to 20 or more and that 5q + r-2s = 0.

In particular, said polyphosphoric acids can be linear compounds of the crude formula PqH ( _{q +} 2) O (3q ₊ i) corresponding to the structural formula:

O

It T

HO - P - O - H

OH ^{q where q has} the definition given above. They can also be products of two-dimensional or three-dimensional structure.

All of these polyphosphoric acids can be considered as polycondensation products by heating aqueous metaphosphoric acid.

It will not be departing from the scope of the invention by combining several different chemical additives such as different organic compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reaction of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), and / or different paraffins and / or different polyphosphoric acids in the bituminous composition of invention.

According to an advantageous embodiment, the bituminous composition comprises at least two chemical additives.

According to a first variant of this embodiment, the bituminous composition comprises at least a first chemical additive of formula (V) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.

Preferably, and according to this first variant, the bituminous composition comprises at least one first chemical additive of formula (V) and at least one second chemical additive of formula (II).

More preferably, and according to this first variant, the bituminous composition comprises at least one first additive of formula (V) and at least one second chemical additive of formula (IIA).

Preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracids (z = 4), preferably from diacids (z = 2).

More preferably, and still according to this first variant, the first chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

Advantageously, and according to this first variant, the first chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid with w = 8.

According to a second variant of this embodiment, the bituminous composition comprises at least a first chemical additive of formula (II) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.

Preferably, and according to this second variant, the first chemical additive of formula (II) is chosen from chemical additives of formula (IIA).

More preferably, and according to this second variant, the bituminous composition comprises at least one first chemical additive of formula (IIA) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (IIB); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second chemical additive being distinct from the first chemical additive.

Even more preferably, and according to this second variant, the bituminous composition comprises at least one first additive of formula (IIA) and at least one second additive of formula (V).

Advantageously, and according to this second variant, the first chemical additive of formula (HA) is N, N’-ethylenedi (stearamide).

Preferably, and according to this second variant, the second additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracids (z = 4), preferably from diacids ( z = 2).

Even more preferably, and still according to this second variant, the second chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8 , undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

According to a third variant of this embodiment, the bituminous composition comprises at least sebacic acid or 1,10-decanedioic acid and at least N, Nethylenedi (stearamide).

According to a fourth variant of this embodiment, the bituminous composition comprises at least a first additive of formula (I) and at least one second chemical additive chosen from: chemical additives of formula (I); chemical additives of formula (II); chemical additives of formula (III); chemical additives of formula (V); chemical additives of formula (VI); chemical additives of formula (VII) and reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV) „the second chemical additive being distinct from the first chemical additive.

Preferably, and according to this fourth variant, the second chemical additive is chosen from chemical additives of formula (II) and chemical additives of formula (V).

Preferably, and according to this fourth variant, the second chemical additive of formula (II) is chosen from chemical additives of formula (IIA).

More preferably, and according to this fourth variant, the second chemical additive of formula (II) is N, N’-ethylenedi (stearamide).

Preferably, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from diacids (z = 2), triacids (z = 3) and tetracids (z = 4), preferably from diacids (z = 2).

Even more preferably, and still according to this fourth variant, the second chemical additive of formula (V) is chosen from adipic acid or 1,6-hexanedioic acid with w =

4, pimelic acid or 1,7-heptanedioic acid with w = 5, suberic acid or 1,8octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, the sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

Advantageously, and still according to this fourth variant, the second chemical additive of formula (V) is sebacic acid or 1,10-decanedioic acid.

Preferably, and according to this fourth variant, the first chemical additive of formula (I) is 2 ', 3-bis [(3- [3, 5-di- / er / -butyl-4-hydroxyphenyl] propionyl)] propionohydrazide.

Preferably, and according to this embodiment, the mass ratio of the first chemical additive relative to the second chemical additive is from 1: 99 to 99: 1, preferably from 1: 9 to 9: 1, even more preferably from 1: 5 to 5: 1.

According to a first embodiment of the invention, the bituminous composition with additives comprises from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2, 8% by mass, and even more preferably from 0.5% to 2.5% by mass of chemical additive relative to the total mass of the bituminous composition.

According to another embodiment of the invention, the bituminous composition with additives according to the invention is a concentrated bituminous composition. In this case, before its implementation, for example in an application described below, the concentrated bituminous composition with additives is melted and then diluted with at least one other bituminous composition without additives. This dilution is calculated to reach an additive content of 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.8% by mass, and even more preferably from 0.5% to 2.5% by mass of chemical additive relative to the total mass of the bituminous composition.

According to this embodiment, the concentrated additive bituminous composition comprises from 5% to 30% by mass, preferably from 6% to 28% by mass, more preferably from 7% to 26% by mass of chemical additive (s) ( s) relative to the total mass of said base of the bituminous composition.

According to one embodiment of the invention, the bituminous composition with additives may further comprise at least one olefinic polymer adjuvant.

The olefinic polymer builder is preferably selected from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) copolymers resulting from the grafting of a monomer B onto a polymer substrate.

(a) The ethylene / (meth) acrylate copolymers are advantageously chosen from random or block copolymers, preferably random, 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 60% to 90% by mass of ethylene.

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

Monomer A is chosen from vinyl acetate and C 1 to C 6 alkyl acrylates or methacrylates. Monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.

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

(c) The copolymers result from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, on a polymer substrate. The polymer substrate consists of a polymer chosen from polyethylenes, in particular low density polyethylenes, polypropylenes, random or block copolymers, preferably random, of ethylene and vinyl acetate and random or block copolymers, preferably random , ethylene and C 1 to C 6 alkyl acrylate or methacrylate, comprising from 40% to 99.7% by mass, preferably from 50% to 99% by mass of ethylene. Said graft copolymers comprise from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of grafted units obtained from monomer B.

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 B monomer chosen from acrylate of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0, 5% to 15% by mass, preferably from 2.5% to 15% by mass of units derived from monomer B, the remainder being formed from units derived from ethylene.

According to one embodiment of the invention, the bituminous composition comprises 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 polymer admixture relative to the total mass of the bituminous composition.

According to a particular embodiment, a solid bituminous composition is prepared in the cold and in divided form by bringing into contact:

- at least one bituminous composition as defined above,

- from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.8% by mass, and even more preferably from 0.5% to 2.5% by mass of at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, the percentages being given by mass relative to the total mass of the bituminous composition.

According to another particular embodiment, a solid concentrated bituminous composition is prepared in the cold and in divided form by bringing into contact:

- at least one bituminous composition as defined above,

- 5% and 30% by mass, preferably 6% and 28% by mass, more preferably 7% and 26% by mass of at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof, the percentages being given by mass relative to the total mass of the bituminous composition.

The amounts of chemical additives and, optionally, of the olefinic polymer additive are adjusted according to the nature of the bituminous composition used.

Method for transporting and / or storing and / or handling the solid bituminous composition when cold and in divided form

Another subject of the invention also relates to a method for transporting and / or storing and / or handling the solid bituminous composition cold and in divided form, said bituminous composition being transported and / or stored and / or handled in the form breads or granules of bituminous composition which are solid at room temperature, in particular at high room temperature. The cold solid bituminous composition in divided form is as described above.

By “ambient temperature” or “high ambient temperature” is meant the temperature resulting from the climatic conditions in which the bitumen is transported and / or stored. More precisely, the ambient temperature is equivalent to the temperature reached during the transport and / or the storage and / or the handling of the bitumen, it being understood that the ambient temperature implies that no heat input is added other than that resulting from weather conditions.

Preferably, the bituminous composition with additives of the invention is transported and / or stored and / or handled at room temperature for a period greater than or equal to 2 months, preferably 3 months.

According to one embodiment of the invention, the bituminous composition with additives of the invention is transported and / or stored at a temperature below 100 ° C. In particular, the transport and / or storage and / or handling temperature corresponds to the ambient temperature. By ambient temperature is meant the temperature which is reached during transport and / or storage of the bituminous composition according to the invention without said bituminous composition being heated by any type of process. Thus, the ambient temperature can reach high temperatures, below 100 ° C, during the summer periods, in particular in the geographical regions with hot climates.

Preferably, the elevated ambient temperature is less than 100 ° C.

Advantageously, the high ambient temperature is 20 ° C to 90 ° C, preferably 20 ° C to 80 ° C, more preferably 30 ° C to 80 ° C.

The cold solid bituminous compositions and in divided form according to the present invention are remarkable in that they allow the transport and / or the storage of cold bituminous composition under optimal conditions, in particular without there being creep of said compositions. solid bituminous materials during their transport and / or storage, even when the ambient temperature is high and without degrading the properties of said bituminous composition, or even improving them.

Bitumen bread

According to one embodiment of the invention, the solid bituminous composition when cold and in divided form is in the form of a bar. For the purposes of the invention, the bituminous composition in the form of a bar is also called "bitumen bar".

By bitumen bread is meant a block of bituminous composition according to the invention having a mass of between 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 25 kg, even more preferably between 10 kg and 30 kg, said block advantageously being parallelepiped, preferably being a block.

The bitumen slab according to the invention preferably has a volume of between 1000 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 bitumen bread is handled manually by one person, the mass of the bituminous composition 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 bitumen roll can vary from 50 to 1000 kg.

The bitumen slab is made from the bituminous composition with additives as described above according to any process known industrially, for example by extrusion, by molding, or according to the manufacturing process described in document US2011 / 0290695.

The bitumen slab is advantageously packaged with a hot-melt film according to any known method, preferably with a film of polypropylene, polyethylene or a mixture of polyethylene and polypropylene. The bituminous composition packaged in a bitumen bar wrapped in a hot-melt film has the advantage of being ready for use, that is to say that it can be directly heated in the melter without prior unpacking, for example for the production of emulsion or optionally introduced directly into the coating unit for the production of mixes. The hot-melt material which melts with the bituminous composition with additives does not affect the properties of said bituminous composition.

The bitumen block according to the invention can also be covered with an anti-caking compound as defined above.

In this variant, the preferences, the advantages, the different embodiments described for the anti-caking compounds also apply.

The bitumen slab according to the invention can also be packaged in a carton according to any known process.

In particular, the bitumen slab according to the invention is packaged in a cardboard box by hot-pouring the bituminous composition according to the invention in a cardboard box, the wall of the internal face of which is siliconized and then cooled, the dimensions of the cardboard being adapted to desired weight and / or volume of bitumen bread.

When the bitumen bar according to the invention is packaged with a hot-melt film or is packaged in a cardboard box, the Applicant has demonstrated that the deterioration of said hot-melt film or of said cardboard during transport and / or cold storage of said bitumen bar according to the invention did not cause creep of the bituminous composition. Therefore, the bitumen blocks according to the invention retain their initial shape and do not stick together during transport and / or cold storage despite the fact that the hot-melt film or the cardboard is damaged. The absence of creep of the bituminous composition in the form of a bar during its transport and / or cold storage is due to the presence of at least one chemical additive within the bituminous composition.

Bitumen granules

According to another embodiment of the invention, the cold solid bituminous composition in divided form is in the form of granules. For the purposes of the invention, the bituminous composition in the form of granules is also called "bitumen granules".

The bitumen 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. More specifically, the bitumen granules according to the invention preferably have a cylindrical or spherical shape.

The size of the bitumen granules can vary depending on the manufacturing process used.

According to one embodiment of the invention, the size of the bitumen granules 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 to 20 mm. For example, the use of a die makes it possible to control the production of granules of a chosen size. A sieving makes it possible to select granules according to their size.

Preferably, the bitumen 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 bitumen granules is such that the longest average dimension is preferably less than 20 mm, more preferably less than 10 mm, even more preferably less than 5 mm.

The bitumen granules are obtained by shaping a bituminous composition with additives according to the invention as described above according to any known process, for example according to the manufacturing process described in document US Pat. No. 3,026,568, document WO 2009 / 153324 or WO 2012/168380. 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 manufacturing process of granules of bituminous composition, in particular molding, extrusion, pelletizing ...

According to one embodiment of the invention, the bitumen granules further comprise at least one anti-caking agent, preferably of mineral or organic origin.

Preferably, the bitumen granules further comprise between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass of the anti-caking agent relative to to the total mass of the bituminous composition with additives to said granules.

In this embodiment, the bitumen granules are prepared from the bituminous composition according to the invention as defined above, said granules being prepared by bringing into contact:

- one or more bituminous compositions with additives according to the invention,

- between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.8% by mass, and even more preferably between 0.5% and 2.5% by mass of at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, relative to the total mass of the bituminous composition additive to said granules, and

- between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass of the anti-caking agent relative to the total mass of the bituminous composition with additives of said granules.

According to one embodiment of the invention, the bitumen granules are covered over at least part of their surface with an anti-caking agent, preferably over their entire surface.

Preferably, the mass of the anti-caking agent covering at least part of the surface of the granules is between 0.2% and 10% by mass, preferably between 0.5% and 8% by mass, more preferably between 0.5% and 5% relative to the total mass of the bituminous composition with additives to said granules.

Advantageously, the mass of the anti-caking agent covering at least part of the surface of the granules is approximately 1% by mass relative to the total mass of the bituminous composition with additives to said granules.

Preferably, the anti-caking agent layer covering the bitumen granules according to the invention is preferably continuous so that at least 90% of the surface of said granules is covered with an anti-caking agent, of preferably at least 95%, more preferably at least 99%.

Also preferably, the average thickness of the anti-caking agent layer is preferably greater than or equal to 20 µm, more preferably between 20 and 100 µm. . Advantageously, the anti-caking agent layer must be thick enough for it to be continuous.

The granules according to the invention are covered with the anti-caking agent according to any known process, for example according to the process described in document US Pat. No. 3,026,568.

By “anti-caking agent” or “anti-caking compound” is meant any compound which limits, reduces, inhibits, delays the agglomeration and / or adhesion of the granules to each other during their transport and / or their storage. at room temperature and which ensures their fluidity during handling.

Preferably, the anti-caking agent is chosen from talc; fines generally less than 125 µm in diameter with the exception of limestone fines, such as siliceous fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of cones of conifers, in particular of 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 oxides of silicon ; plastic powder; lime; the plaster ; rubber powder; powder of polymers such as styrene-butadiene (SB) copolymers, styrene butadiene-styrene (SBS) copolymers; and their mixtures.

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

For example, the anti-caking agent can be silica fumes. The silica fumes used in the invention are commercially available and for example can be sold by Evonik Degussa under the trademark AEROSIL®, such as for example AEROSIL®200, by Cabot

Corporation under the CAB-O-SIL® and CAB-O-SPERSE® brands or by Wacker Chemie AG under the HDK® brand.

Preferably, the anti-caking compound is chosen from silica fumes.

For the purposes of the invention, the compounds "silica fume" and "fumed silica" have the same chemical definition and are registered under the same CAS number 112 945-52-5. Therefore, within the meaning of the invention, these compounds can be used interchangeably

By “fumed silica” is meant either a fumed silica or a derivative of fumed silica. By “fumed silica” is meant a compound obtained by the vapor phase hydrolysis of chlorosilanes, such as silicon tetrachloride, in a flame of oxygen and hydrogen. Such processes are generally designated as pyrogenic processes, the overall reaction of which is: SiCl1 + H ₂ + O ₂ -> SiO ₂ + 4 HCl.

Fired silicas are distinguished from other silicon dioxide in that they exhibit an amorphous structure. High purity (> 99.8% silica), they have a low hydrophilicity (no microporosity).

Preferably, the fumed silica compound is fumed silica.

According to one embodiment of the invention, the fumed silica compound has a specific surface area of between 25 and 420 m ² / g, preferably between 90 and 330 m ² / g, more preferably between 120 and 280 m / g.

The specific surface of the fumed silica defined in m ² / g commonly called “surface area” or “SA” is measured according to the method of S. Brunauer, PH Emmet and I. Teller, J. Am. Chemical Society, 60: 309 (1938) (BEL).

According to one embodiment of the invention, the fumed silica compound has an average particle size of between 5 and 50 nm.

According to one embodiment of the invention, the fumed silica compound has a pH of between 3 and 10 when it is in the aqueous phase.

According to one embodiment of the invention, the fumed silica compound has a carbon content of between 0.1 and 10% by weight relative to the total weight of the fumed silica compound.

According to one embodiment of the invention, the fumed silica compound is chosen from a hydrophilic fumed silica compound, a hydrophobic fumed silica compound and mixtures thereof.

Preferably, the fumed silica compound is a hydrophilic fumed silica compound. By "hydrophilic" is meant a compound which is miscible with water in all proportions.

The fumed silica compound, or derivative of fumed silica, used within the meaning of the invention can be chemically modified.

Different types of fumed silica compounds are described in the following patent applications and can be used in the present invention:

- silanized pyrogenic silicas, as described in WO 2004/020532, or in WO 2007/128636,

- hydrophilic pyrogenic silicas, as described in WO 2009/071467, WO 2011/000133 filed in the name of Degussa AG or Degussa Gmbh,

- silica fumes made hydrophobic by treatment with polysiloxanes as described in WO 2008/141932, or by silanization as described in WO 2008/141930,

- silicas doped with potassium oxide as described in WO 2008/043635, WO 2008/022836,

- silicas in the form of aggregates of primary particles as described in WO 2009/015969 filed in the name of Evonik Degussa Gmbh or in WO 2010/028261 filed in the name of Cabot Corporation.

The fumed silica compound can be used alone or as a mixture within a coating composition.

Whether it is used alone or as a mixture in a composition, the fumed silica compound can be used in the process according to the invention in the form of a powder or as a dispersion in a solvent which evaporates afterwards. application.

Preferably, when the coating composition comprises at least one fumed silica compound and at least one solvent, the coating composition comprises from 5 to 70% by weight of fumed silica compound relative to the total weight of the composition, more preferably from 20 to 40% by weight.

Preferably, the solvent is an organic solvent or water. By organic solvent is meant any solvent immiscible with a bitumen, such as an alcohol, for example ethanol.

According to one embodiment of the invention, the anti-caking agent included in the bituminous composition forming the bitumen granules may be identical or different from the anti-caking agent covering at least part of the surface of said bitumen granules.

According to one embodiment of the invention, the bitumen granules comprise a core and a coating layer in which:

- the core comprises at least one bituminous composition with additives according to the invention as defined above and,

the coating layer comprises at least one viscosifying compound and at least one anti-caking compound as defined above.

The term “coating layer” is understood to mean that the coating layer covers at least 90% of the surface of the heart, preferably at least 95% of the surface of the heart, more preferably at least 99% of the surface of the heart.

By "viscosifier" or "viscosifier compound" is meant a compound which has the property of reducing the fluidity of a liquid or of a composition and therefore of increasing its viscosity.

The "viscosifying" and "viscosifying compound" outfits are used within the meaning of the invention, in an equivalent manner and independently of one another.

The viscosifier within the meaning of the invention is a material which has a dynamic viscosity greater than or equal to 50 mPa.s ′ ¹ , preferably from 50 mPa.s ′ ¹ to 550 mPa.s ′ ¹ , more preferably from 80 mPa.s ′ 1. s ' ¹ to 450 mPa.s' ¹ , the viscosity being a Brookfield viscosity measured at 65 ° C. The viscosity of a viscosifier according to the invention is measured at 65 ° C. using a Brookfield CAP 2000+ viscometer and at a speed of rotation of 750 rpm. The measurement is read after 30 seconds for each temperature.

Preferably, the viscosifier is chosen from:

gelling compounds, preferably of plant or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives, starches, modified starches, or gellan gums;

- Polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g-mol ' ¹ and 8000 g.mol' ¹ , such as for example a PEG having a molecular weight of 800 g.mol ' ¹ (PEG- 800), a PEG having a molecular weight of 1000 g.mol ' ¹ (PEG-1000), a PEG having a molecular weight of 1500 g.mol' ¹ (PEG-1500), a PEG having a molecular weight of 4000 g .mol ' ¹ (PEG-4000) or a PEG having a molecular weight of 6000 g.mol' ¹ (PEG-6000);

- mixtures of such compounds.

Advantageously, the viscosifier is chosen from:

gelling compounds, preferably of plant or animal origin, such as: gelatin, agar-agar, alginates, cellulose derivatives or gellan gums;

- polyethylene glycols (PEG) such as PEGs having a molecular weight of between 800 g-mol ¹ and 8000 g.mol ' ¹ , such as for example a PEG having a molecular weight of 800 g-mol' ¹ (PEG-800 ), a PEG having a molecular weight of 1000 g.mor ¹ (PEG-1000), a PEG having a molecular weight of 1500 g.mol ' ¹ (PEG-1500), a PEG having a molecular weight of 4000 g.mor ¹ (PEG-4000) or a PEG having a molecular weight of 6000 g.mor ¹ (PEG-6000);

- mixtures of such compounds.

According to one embodiment of the invention, the coating layer is obtained by applying a composition comprising at least one viscosifying compound and at least one anti-caking compound on all or part of the surface of the core in solid bituminous composition.

Preferably, the coating layer is solid at room temperature, including at elevated room temperature.

Preferably, the composition comprising at least one viscosifying compound and at least one anti-caking compound has a viscosity greater than or equal to 200 mPa.s ' ¹ , preferably between 200 mPa.s' ¹ and 700 mPa.s ¹ , the viscosity being a Brookfield viscosity. Preferably, the coating layer comprises at least 10% by mass of at least one viscosifying compound relative to the total mass of the coating layer, preferably from 10 to 90% by mass, more preferably from 10 to 85% by mass. mass.

Advantageously, when the viscosifier is a gelling agent, such as for example gelatin, the coating layer comprises from 10 to 90% by mass of viscosifying compound relative to the total mass of the coating layer, preferably from 15 to 85% , even better from 15 to 60%.

Advantageously, when the vicosifier is a gelling agent, such as for example gelatin, the coating layer comprises from 10 to 90% by mass of anti-caking compound relative to the total mass of the coating layer, preferably from 15 to 85%, even better 40 to 85%.

Advantageously, when the vicosifier is a PEG, such as for example a PEG having a molecular weight of between 800 g.mol ' ¹ and 8000 g.mol' ¹ , the coating layer comprises from 10 to 90% by mass of viscosifying compound by relative to the total mass of the coating layer, preferably 40 to 90%, even better still 60 to 90%.

Advantageously, when the vicosifier is a PEG, such as for example a PEG having a molecular weight of between 800 g.moP ¹ and 8000 g.mol ' ¹ , the coating layer comprises from 10 to 90% by mass of anti-caking compound relative to the total mass of the coating layer, preferably 10 to 60%, even better still 10 to 40%.

Preferably, the coating layer comprises at least 10% by mass of an anti-caking compound relative to the total mass of the coating layer, preferably from 10 to 90% by mass, even more preferably from 15 to 90% en masse.

Preferably, the coating layer represents at least 5% by mass relative to the total mass of the granule, preferably from 10 to 60% by mass, more preferably from 10 to 50%.

Advantageously, the viscosifying compound and the anti-caking compound represent at least 90% by mass relative to the total mass of the coating layer, even better at least 95% by mass and advantageously at least 98% by mass.

According to a preferred embodiment, the coating layer consists essentially of the viscosifying compound and of the anti-caking compound.

In addition to the viscosifying compound and the anti-caking compound, the coating layer may optionally comprise one or more compounds chosen from: chemical additives, polymers, etc.

According to a preferred embodiment of the invention, the bitumen granules have:

a core comprising at least one bituminous composition according to the invention as defined above and, a coating layer comprising gelatin or a PEG and at least one anti-caking compound chosen from fines generally with a diameter of less than 125 μm ; wood residues such as lignin, conifer needle powders and conifer cone powders; rubber crumb; powder of SBS copolymers; silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas; and their mixtures.

More preferably, the bitumen granules have:

a core comprising at least one bituminous composition according to the invention as defined above and,

a coating layer comprising gelatin or a PEG and at least one anti-caking compound chosen from fines generally with a diameter of less than 125 μm; lignin; rubber crumb; silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas; the powder of SBS copolymers.

According to a still preferred embodiment, the bitumen granules essentially consist of:

- a core consisting of a bituminous composition with additives according to the invention as defined above and,

- a coating layer consisting of a mixture of gelatin or a PEG, with at least one anti-caking compound chosen from fines generally with a diameter of less than 125 μm; lignin; rubber crumb; powder of SBS copolymers; silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas.

Preferably, the bitumen granules essentially consist of:

a core consisting of an additive bituminous composition as defined above comprising at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, and

- a coating layer consisting of a mixture of gelatin or a PEG, with at least one anti-caking compound chosen from fines generally with a diameter of less than 125 μm; lignin; rubber crumb; powder of SBS copolymers; silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas.

According to another still preferred embodiment, the bitumen granules essentially consist of:

a core consisting of a bituminous composition with additives according to the invention as defined above, comprising a chemical additive of formula (I) defined below and a coating layer consisting of a mixture of gelatin or of a PEG , with at least one anti-caking compound chosen from fines generally with a diameter of less than 125 μιη; lignin; rubber crumb; powder of SBS copolymers; silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas.

According to another still preferred embodiment, the bitumen granules essentially consist of:

a core consisting of a bituminous composition with additives according to the invention as defined above, comprising a chemical additive of formula (I) defined below and a coating layer consisting of a mixture of gelatin or of a PEG , with at least one anti-caking compound chosen from silica fumes, in particular hydrophilic and hydrophobic silica fumes; pyrogenic silicas, in particular hydrophobic or hydrophilic pyrogenic silicas.

According to one embodiment of the invention, the bitumen granules may further comprise one or more other coating layers, based on anti-caking agent covering all or part of the coating layer of the cold solid bituminous composition. according to the invention.

Cold solid bitumen kit in divided form

Another object of the invention relates to a kit comprising at least:

- a solid bitumen base cold and in divided form as defined above,

- a capsule comprising a pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427 in the form of granules.

Such a kit allows the manufacture of a bituminous composition according to the invention under easier processing conditions. In particular, the proportion of solid bitumen base when cold and in divided form and of pitch is calculated during the manufacture of the kit, which avoids having to dose the amount of pitch during the manufacture of the bituminous composition.

According to one embodiment of the invention, the cold solid bitumen base in divided form is a bitumen base comprising at least one additive as defined above.

According to a particular embodiment, a solid bitumen base is prepared in the cold and in divided form by bringing into contact:

at least one bitumen base as defined above, from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.8% by mass , and even more preferably from 0.5% to 2.5% by mass of at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, the percentages being given by mass relative to the mass total bitumen base.

According to one embodiment of the invention, the cold solid bitumen base in divided form is in the form of a bar.

The embodiments described above for bitumen bread also apply to bitumen base bread.

According to one embodiment of the invention, the bitumen base in the form of a bar comprises on one of its faces a cavity making it possible to accommodate all or part of the capsule.

According to one embodiment of the invention, the capsule is housed in whole or in part in the cavity in a removable manner.

According to this embodiment, the capsule may be a capsule with a soft envelope, in particular a sachet, or a capsule with a hard envelope.

Preferably, the capsule is made of hot-melt plastic film, in particular of polyethylene, or of silicone.

Another object of the invention relates to the use of the kit as defined above in the process for preparing a bituminous composition ready for application according to the invention.

According to one embodiment of the invention, the bitumen base in the form of a bar and the capsule forming the kit as defined above are used in the process for preparing a bituminous composition simultaneously or consecutively.

In a variant, when the bitumen base in the form of a bar and the capsule forming the kit as defined above are used consecutively in the process for preparing a bituminous composition, said bitumen base in the form of a bar is heated beforehand then the capsule is added. In this variant, before heating the bitumen base bread, the capsule is dislodged from the cavity on one side of the bread.

In another variant, the bitumen base in the form of a bar and the capsule forming the kit as defined above are used simultaneously in the process for preparing a bituminous composition.

Bituminous mixes or bituminous concrete

The invention relates to the use of the bituminous composition according to the invention as defined above for the manufacture of bituminous mixes or bituminous concretes.

The invention also relates to bituminous mixes or bituminous concretes comprising the composition according to the invention as defined above and aggregates.

The invention also relates to a process for manufacturing bituminous mixes or bituminous concretes comprising at least one bituminous composition and aggregates, the bituminous composition being chosen from solid bituminous compositions under cold conditions and in divided form according to the invention as defined. above, this method comprising at least the steps of:

- heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C,

- mixing the aggregates with the bituminous composition in a tank such as a mixer or a mixer drum,

- obtaining of asphalt.

The method of the invention has the advantage of being able to be implemented without a prior step of heating the granules of solid bitumen. According to one embodiment of the invention, the process does not include a step of heating the solid bituminous composition cold and in divided form before it is mixed with the aggregates.

The mix manufacturing process according to the invention does not require a step of heating the solid bituminous composition before mixing with the aggregates because, in contact with the hot aggregates, the bitumen which is solid at room temperature melts.

The bitumen which is solid at room temperature according to the invention as described above has the advantage of being able to be added directly to the hot aggregates, without having to be melted before mixing with the hot aggregates.

Preferably, the step of mixing the aggregates and the road binder is carried out with stirring, then the stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow a homogeneous mixture to be obtained.

The solid bitumen according to the present invention is remarkable in that it allows the transport and / or the storage of road bitumen at room temperature under optimal conditions, in particular without there being agglomeration and / or adhesion of the solid bitumen during transport and / or storage, even when the ambient temperature is high.

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

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

Experimental part :

Material and methods

The properties of bitumens are measured using the methods described below:

- Needle penetration at 25 ° C (P25): unit = l / 10mm, standard EN 1426.

- Ball and ring softening temperature (TBA): unit = ° C, standard EN1427.

- Fraass fragility point (Fraass): unit = ° C, standard EN12593

- Complex G * modulus of the bituminous composition measured at 15 ° C and 60 ° C and at a frequency of 10Hz: unit = MPa or Pa, standard EN 14770

- Complex modulus of stiffness of asphalt mixes measured at 15 ° C and at a frequency of 10Hz: unit = MPa, standard EN 12697-24-26

Raw materials :

- Bitumen base (B): several bitumen bases were used, the characteristics of which are presented below in Table 1:

Trade name or composition Penetration P25 TBA B1 Azalt ® 50/70 (bitumen base) 50 51.1 ° C B2 Azalt ® 35/50 (bitumen base) 40 51.6 ° C B3 Bitumen base of Ghanaian origin 125 42.0 ° C B4 Bitumen base of Ghanaian origin 89 45.6 ° C B5 Stelox®l 10/30 (oxidized bitumen) 25 113 B6 Modulotal® (hard grade bitumen used for the manufacture of high modulus asphalt) 16 65.4

Table 1: characteristics of bitumen bases tested

Gilsonite (G) sold commercially by Hillington under the brand name H103 M®

Pitch (BR): several pitches were used, the characteristics of which are presented below in Table 2:

Penetrability P25 TBA BRI 0-2 115-125 ° C BR2 0-2 135-145 ° C BR3 0-2 165-175 ° C

Table 2: characteristics of the pitches tested

I - Preparation of the compositions according to the invention and of the control compositions:

From bitumen bases B1 to B6 and pitches BRI to BR3 or from Gilsonite G, bituminous compositions were prepared according to the following protocol:

The bitumen base BX (X = 1 to 4) was brought to 180 ° C and pitch (or Gilsonite or base B5 or B6) was added at a temperature of 180 ° C. The mixture was kept stirred at 180 ° C for 1 hour and 300 rpm.

The compositions C1 to C10 thus obtained are summarized in Table 3A below. The contents are given in mass relative to the total mass of the composition:

Composition Cl C2 C3 C4 C5 C6 C7 C8 C9 CIO B1 88% 88% - - - - - - - - B2 - - 95% 85% 90% 80% - - - - B3 - - - - - - 95% - 97% - B4 - - - - - - - 95% - 97% BRI 12% - - - - - - - - - BR2 - 12% - - 10% 20% 5% 5% - - BR3 - - 5% 15% - - - - 3% 3%

Table 3 A: Bituminous compositions according to the invention

The compositions T1 to T3 thus obtained are summarized in Table 3B below. The contents are given in mass relative to the total mass of the composition:

Composition Tl T2 T3 B1 61% 88% 88% B5 - 12% - B6 39% - - G - - 12%

Table 3 B: Control bituminous compositions

Compositions C1 to C10 as well as control compositions T1 and T2 exhibit homogeneous appearances after their manufacture.

The control composition T3 has a non-homogeneous (two-phase) appearance with the presence of deposits at the bottom of the tank after their manufacture. Therefore, the use of gilsonite to harden bitumens is not recommended due to the non-homogeneous appearance of the resulting composition. The mechanical property tests could therefore not be carried out on this T3 control composition.

II - Measurements of the mechanical properties of the compositions according to the invention, bitumen bases and control compositions:

The properties of penetrability, of softening point, of Fraass as well as of the modulus G * at a frequency of 10 Hz and respectively at temperatures of 15 ° C and 60 ° C were measured for compositions C1 to CIO, bitumen bases. B1 to B6 and the control compositions T1 to T3.

The properties of compositions C1 to CIO as well as the properties of bitumen bases B1 to

B6 and control compositions T1 to T3 are summarized in Tables 4A and 4B below:

Composition Cl C2 C3 C4 C5 C6 C7 C8 C9 CIO Penetration (1/10 mm) 30 30 28 16 26 19 86 62 87 64 TBA (° C) 58.2 58.6 55.6 63.6 58.6 64.2 47.2 50.6 46.6 50.2 G * (MPa) (15 ° C, 10Hz) 28.2 28.3 69 96 76 105 8.0 12.4 7.2 9.7 G * (Pa) (60 ° C, 10Hz) 5380 0 5780 0 nd nd nd nd nd nd nd nd

Table 4 A: Mechanical properties of compositions C1 to CIO nd: property not determined

Composition B1 B2 B3 B4 B5 B6 Tl T2 Penetrability (1/10 mm) 50 40 125 89 25 16 30 42 TBA (° C) 51.1 51.6 42 45.6 113 65.4 58.2 54.6 G * (MPa) (15 ° C, 10Hz) 21.4 54 5.7 9.1 12.2 47 39.8 19.1 G * (Pa) 24000 nd nd nd nd nd nd 27500

(60 ° C, 10Hz)

Table 4 B: Mechanical properties of bitumen bases B1 to B6 and witnesses T1 to T3 nd: property not determined

Mechanical properties of compositions C1 to CIO, bitumen bases B1 to B6 and controls T1 to T3 after aging.

It is noted that the addition of a pitch according to the invention in a bitumen base of softer grade such as Azalt® 50/70 or Azalt® 35/50 leads to a hardening of this base which results in particular by lowering the penetrability and increasing the TBA (compositions C1, C2, C3, C5):

i) from 50 to 30 1/10 mm and from 51.1 to 58.2 ° C or 58.6 ° C for Azalt® 50/70 in the presence of 12% pitch, ii) from approximately 40 to 28 1/10 mm and about 51.6 to 55.6 ° C for Azalt® 35/50 in the presence of 5% pitch, iii) about 40 to 26 1/10 mm and about 51.6 to 58.6 ° C for Azalt® 35/50 in the presence of 10% pitch, which makes it possible to formulate a composition meeting the specifications in terms of penetrability and TBA at a composition of grade 20/30 , from a grade 50/70 or 35/50.

It is also noted that the addition of a pitch according to the invention in a bitumen base of softer grade such as Azalt® 35/50 leads to a hardening of this base which results in particular in a lowering of the penetrability and / or an increase in TBA (compositions C4 and C6):

i) about 40 to 16 1/10 mm and about 51.6 to 63.6 ° C for Azalt® 35/50 in the presence of 15% pitch (BR3), ii) about 40 at 19 1/10 mm and about 51.6 at 64.2 ° C for Azalt® 35/50 in the presence of 20% pitch (BR2), which makes it possible to formulate a composition meeting the specifications in terms of of penetrability and TBA to a composition of grade 10/20, from grade 35/50.

It is noted that the addition of a pitch according to the invention in a bitumen base of a softer grade such as Azalt® 50/70 or Azalt® 35/50 leads to a significant increase in the G * modulus of the composition:

i) for a 50/70 grade bitumen, its modulus goes from 21.4 MPa to a modulus beyond 28 MPa with the addition of 12% pitch according to the invention, ii) for a 35 grade bitumen / 50, its modulus goes from 54 to a modulus of 69 and 105 MPa depending on the amount of pitch according to the invention added.

Comparatively, it is observed that the addition of Modulotal 10/20 in a bitumen base of softer grade such as Azalt 50/70 leads to a hardening of this base which results in particular in a lowering of the penetrability and an increase in the TBA (composition Tl):

i) from 50 to 30 1/10 mm and from 51.1 to 58.2 ° C for Azalt® 50/70 in the presence of 39% Modulotal®! 0/20, which makes it possible to formulate a composition meeting the specifications in terms of penetrability and TBA at a 20/30 grade composition, starting from a 50/70 grade.

Regarding the modulus, the addition of Modulotal ® in a softer grade bitumen base such as Azalt® 50/70 leads to a significant increase in the G * modulus of the composition:

i) for a 50/70 grade bitumen, its modulus goes from 21.4 MPa to a modulus beyond about 40 MPa with the addition of 39% modulotal.

However, at iso-penetrability, that is to say in order to obtain a 20/30 grade composition, from a 50/70 grade, it is necessary to use at least three times as much hard bitumen Modulotal® 10/20 than pitch, which represents greater complexity in terms of hard bitumen logistics.

Comparatively, it is observed that the addition of Stelox®l 10/30 in a bitumen base of a softer grade such as Azalt® 50/70 leads to a hardening of this base which results in particular in a lowering of the penetrability and an increase in TBA (T2 composition):

i) from 50 to 42 1/10 mm and from 51.1 to 54.6 ° C for Azalt® 50/70 in the presence of 12% of Stelox®l 10/30, which makes it possible to formulate a composition responding to specifications in terms of penetrability and TBA at a composition of grade 35/50, from grade 50/70.

However, with an iso-content of Stelox® and pitch, that is to say with 12% of Stelox® in the control composition T2 and 12% of pitch in the composition C1, one obtains from a bitumen of grade 50/70, a grade 35/50 composition using Stelox ® while using pitch, a grade 20/30 composition is obtained from a grade 50/70 bitumen.

It is also noted that the addition of 12% of Stelox ® in a 50/70 grade bitumen does not improve the modulus of this bitumen but on the contrary lowers its modulus because it drops from 21.4 MPa to 19, 1 MPa unlike the addition of pitch in a grade 50/70 bitumen.

Therefore, these results demonstrate that at iso-content of Stelox ® and pitch, a bitumen comprising 12% pitch has a harder grade and also a higher modulus than a bitumen comprising 12% Stelox ®.

It is also noted that the addition of a pitch according to the invention in a bitumen base B3 of softer grade leads to a hardening of this base which results in particular in a lowering of the penetrability and / or an increase of the TB A. :

i) from 125 to 86 1/10 mm and from 42 to 47.2 ° C for the bitumen base B3 in the presence of 5% of BR2 pitch (composition C7), ii) from 125 to 87 1/10 mm and 42 at 46.6 ° C for the bitumen base B3 in the presence of 3% of BR3 pitch (composition C9), which makes it possible to formulate a composition meeting the specifications in terms of penetrability with a composition having a penetrability of less than 90 1/10 mm and meeting the specifications of grade AC 10.

It is also noted that the addition of a pitch according to the invention in a softer grade B4 bitumen base leads to a hardening of this base which results in particular in a lowering of the penetrability and / or an increase in the TBA:

i) from 89 to 62 1/10 mm and from 45.6 to 50.6 ° C for the bitumen base B4 in the presence of 5% of BR2 pitch (composition C8), ii) from 89 to 64 1/10 mm and from 45.6 to 50.2 ° C for the bitumen base B4 in the presence of 3% of BR3 pitch (CIO composition), which makes it possible to formulate a composition meeting the specifications in terms of penetrability with a composition having a penetrability of less than 70 1/10 mm and meeting the specifications of grade AC20.

It can be seen that the addition of a pitch according to the invention in a bitumen base of a softer grade such as B3 or B4 bitumen bases leads to a significant increase in the G * modulus of the composition:

i) for the bitumen base B3, its modulus goes from 5.7 to a modulus of between 7.2 and 8 MPa depending on the amount of pitch according to the invention added, ii) for the bitumen base B4, its modulus goes from 9 to a modulus of between 9.7 and 12.4 MPa depending on the amount of pitch according to the invention added.

Consequently, the addition of pitch according to the invention in a bitumen base makes it possible both to obtain a harder grade bitumen base and also to obtain a bitumen base having a high modulus which makes it possible to reuse for the manufacture. of high modulus asphalt.

III - Preparation of bituminous mixes and measurements of their mechanical properties:

A bituminous mix is characterized as a high modulus bituminous mix also called EME according to standard NF EN 13108-1 if it has at least one complex modulus of rigidity greater than 14,000 MPa, the measurement being carried out measured at 15 ° C and at a frequency of 10Hz according to standard NF EN 12697-26.

Two bituminous mixes (El and E2) are respectively obtained from the bitumen base B1 and from the composition C2 according to the invention and from aggregates having the granular cut described in Table 5:

Cut (mm) 0/2 2/6 6/10 10/14 Filler Weight (%) 31 18 20 29 2

Table 5: Particle size composition

Bituminous mixes are prepared as follows:

The aggregates are brought to a temperature of 165 ° C. for a period of approximately 8 hours. The bituminous composition is heated to 165 ° C. then poured onto the previously heated aggregates, the mixture thus obtained is kneaded for approximately 180 seconds at 165 ° C.

The bituminous mixes thus obtained have a bituminous composition content of 5.1% by mass relative to the total mass of the mixes.

The bituminous mixes El and E2 are obtained according to the method described above and respectively comprise 5.1% by mass of bitumen base B1 and of composition C2 according to the invention relative to the total mass of the mixes.

The complex stiffness moduli of bituminous mixes E1 and E2 are summarized in Table 6 below.

El E2 Complex modulus at 15 ° C and 10Hz (MPa) 11493 14608

Table 6: Complex modulus of stiffness of bituminous mixes El and E2

The bituminous mixes E2 obtained from composition C2 according to the invention have a complex modulus of 14608 MPa, unlike the bituminous mixes E1 obtained from the bitumen base of grade 50/70, the complex modulus of which is 11493 MPa.

Therefore, E2 bituminous mixes with a modulus value greater than 14000 Pa can be used as high modulus bituminous mixes unlike El bituminous mixes.

IV - Preparation of the various cores of granules of bituminous composition

4.1 Preparation of the bituminous composition with additives

The bituminous composition with additives C2 ’is prepared from the C2 composition prepared above and 1.10 decanedioic acid, noted Additive Al.

The quantities in percentage by mass used for the preparation of the bituminous composition with C2 ’additives are shown in Table 7 below.

Additive composition C2 ’ Composition C2 98.5% Al additive 1.5%

Table 7

The C2 ’bituminous composition is prepared as follows.

Composition C2 is introduced into a reactor maintained at 160 ° C. with stirring at 300 revolutions / min for two hours. The additive Al is then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.

The cores of granules G ₂ are prepared from the bituminous composition with additives C2 ′ according to one of the following protocols.

4.2 General method for the preparation of the cores in bituminous composition G ₂ of the granules according to the invention

The C2 ′ bituminous composition base is heated at 170 ° C for two hours in an oven before being poured into a silicone mold having various spherically shaped holes so as to form the bituminous composition cores. After observing the solidification of the bituminous composition in the mold, the surplus is leveled with a blade heated with a bunsen burner. After 30 minutes, the solid bituminous composition in the form of uncoated granules is removed from the mold and stored in a tray covered with silicone paper.

4.3 General method for the preparation of the cores in bituminous composition Gj of the granules according to the invention with an industrial process

For the implementation of this method, it is possible to use a device and a method as described in great detail in US Pat. No. 4,279,579. Various models of this device are available commercially from the company Sandvik under the trade name of. Rotoform.

G ₂ granules of bituminous composition can also be obtained from the bituminous composition with additives C2 'poured into the reservoir of such a device and maintained at a temperature of between 130 and 270 ° C.

One or more injection nozzles allow (tent) the transfer of the bituminous composition with additives C2 'inside the double pastillation drum comprising a rotating external drum, the two drums being equipped with slots, nozzles and orifices allowing the pastillation of drops of bituminous composition through the first fixed drum and orifices having a diameter of between 2 and 10 mm of the rotating outer drum. The drops of bituminous composition are deposited on the upper face of a horizontal tread driven by rollers.

V- General method for the preparation of granules of solid bituminous composition according to the invention comprising a coating layer composed of at least one anti-caking compound

The granules of additivated bituminous composition obtained according to methods 4.2 and 4.3 are left at room temperature for 10 to 15 minutes. The granules thus formed are coated on their surface with an anti-caking compound, then sieved to remove the excess anti-caking compound.

The granules G ₂ ′ are prepared from the granules G ₂ obtained previously and according to the method described above, using as anti-caking compound pyrogenic silica available commercially under the reference AEROSIL 200.

The percentage by weight of the coating for the granules G ₂ ′ is approximately 1% by weight relative to the total weight of the bitumen of the granules.

It can be seen that the granules obtained have the advantage of being easily transportable and have good storage resistance.

Claims (20)

1. Bituminous composition in cold solid form and in divided form characterized in that the composition comprises: a) at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427, and b) at least one bitumen base. 2. The composition of claim 1, wherein the pitch is an oxidized pitch. 3. Composition according to claim 1 or 2, in which the pitch is present in an amount ranging from 2 to 30% by mass relative to the total mass of the composition. 4. Bituminous composition according to any one of claims 1 to 3, which is cold solid and in divided form, and further comprises at least one chemical additive selected from an organic compound, a paraffin, a polyphosphoric acid and mixtures thereof. 5. Bituminous composition according to claim 4 comprising from 0.1% to 5% by mass, preferably from 0.5% to 4% by mass, more preferably from 0.5% to 2.8% by mass, and again more preferably from 0.5% to 2.5% by mass of said chemical additive relative to the total mass of the bitumen base. 6. Bituminous composition according to claim 4 or 5, in which the chemical additive is an organic compound which has a molar mass by mass of less than or equal to 2000 gmol ' ¹ , preferably a molar mass of less than or equal to 1000 gmol' ^1. . 7. A bituminous composition according to any one of claims 4 to 6, in the form of a bar or granules. 8. A method of manufacturing a bitumen composition according to any one of claims 1 to 7, this method comprising the following steps: - Heating of the bitumen base b) to a temperature ranging from 140 to 180 ° C, - Introduction of pitch a) into the bitumen base b), - Stirring the mixture at a temperature ranging from 140 to 180 ° C until a homogeneous mixture is obtained. 9. The method of claim 8, wherein the pitch is introduced in the form of granules. 10. Kit capable of being used for the manufacture of a bituminous composition according to any one of claims 1 to 7, comprising at least: - a solid bitumen base cold and in divided form, - a capsule comprising at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427 in the form of a granule. 11. Kit according to claim 10, in which the solid bitumen base under cold conditions and in divided form is in the form of a bar. 12. Kit according to claim 10 or 11, wherein the solid cold bitumen base and in divided form comprises on one of its faces, a cavity allowing all or part of the capsule to be accommodated. 13. Kit according to claim 12, wherein the capsule is housed in whole or in part in said cavity in a removable manner. 14. A method of preparing a bituminous composition according to any one of claims 4 to 7, comprising: - the mixture of at least one bituminous composition according to any one of claims 1 to 3 and at least one chemical additive chosen from an organic compound, a paraffin, a polyphosphoric acid and their mixtures, to form an additive bituminous composition , - shaping of the bituminous composition with additives in the form of bread or granules. 15. A method of transporting and / or storing and / or handling a bituminous composition according to any one of claims 4 to 7, said bituminous composition being transported and / or stored and / or handled in the form of bars or bars. granules of bituminous composition which are solid at room temperature. 16. Asphalt mixes or bituminous concretes comprising the bituminous composition according to any one of claims 1 to 7 and aggregates. 17. Use of a bituminous composition according to any one of claims 1 to 7 for the manufacture of bituminous mixes or bituminous concretes. 18. A method of manufacturing bituminous mixes or bituminous concretes comprising at least one bituminous composition and aggregates, the bituminous composition being chosen from solid bituminous compositions under cold conditions and in divided form according to any one of claims 4 to 7, this process comprising at least the steps of: - heating of the aggregates to a temperature ranging from 100 ° C to 180 ° C, - mixing the aggregates with the bituminous composition in a tank such as a mixer or a mixer drum, - obtaining of asphalt. 19. The method of claim 18, which does not include a step of heating the solid bituminous composition cold and in divided form before mixing with the aggregates. 20. Use of a pitch having a penetrability at 25 ° C ranging from 0 to 20 1/10 mm, a ball and ring softening temperature (TBA) ranging from 115 ° C to 175 ° C, it being understood that the penetrability is measured according to standard EN 1426 and that the TBA is measured according to standard EN 1427 to increase the modulus of a bituminous composition or to increase the modulus of asphalt mixes or asphalt concrete.