EP3551700A1

EP3551700A1 - Bitumen solid at ambient temperature

Info

Publication number: EP3551700A1
Application number: EP17816996.7A
Authority: EP
Inventors: Mouhamad MOUAZEN
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Onetech SAS
Priority date: 2016-12-07
Filing date: 2017-12-06
Publication date: 2019-10-16
Also published as: FR3059674B1; US20190330472A1; US11292912B2; FR3059674A1; WO2018104660A1; SA519401931B1

Abstract

The invention relates to bitumen granules comprising a core and a coating layer, in which the core comprises at least one bitumen base, and the coating layer comprises at least: one oil selected from a hydrocarbon oil of petroleum or synthetic origin; and at least one organogelator compound selected from among compounds of general formula (I), (II) or (V). The invention also relates to a method for producing bitumen granules, as well as to the use thereof as an asphalt binder, in particular for producing mixes. The invention further relates to a method for producing mixes from bitumen granules and also to a method for transporting and/or storing and/or handling bitumen granules.

Description

SOLID BITUMEN AT AMBIENT TEMPERATURE

Technical area

The present invention relates to a bitumen composition in divided form, solid at room temperature. The present invention also relates to a process for preparing a solid bitumen composition at ambient temperature and its use as a road binder, in particular for the manufacture of asphalt.

The present invention also relates to a method for manufacturing asphalt from solid bitumen according to the invention and a method for transporting and / or storing and / or handling a solid bitumen composition at room temperature according to the invention. 'invention.

State of the art

The vast majority of bitumen is used in construction, mainly for the manufacture of road pavements or in industry, for example for roofing applications. It is generally in the form of a highly viscous black material, even solid at room temperature, which becomes fluid upon heating.

In general, bitumen is stored and transported hot, in bulk, in tanker trucks or by boats at high temperatures in the range of 120 ° C to 160 ° C. However, the storage and transport of hot bitumen have certain disadvantages. On the one hand, the transport of hot bitumen in liquid form is considered dangerous and it is very framed from a regulatory point of view. This mode of transport presents no particular difficulties when the equipment and the transport infrastructures 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 trip too long. Delivery distances for bitumen are therefore limited. On the other hand, the maintenance of bitumen at high temperatures in tanks or tank trucks consumes energy. In addition, maintaining the bitumen at elevated temperatures for a long time may affect the properties of the bitumen and thus change the final performance of the bitumen.

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

As an example of packaging for the cold transport currently used, there may be mentioned the packaging of bitumen at room temperature in metal drums. This means is increasingly questionable from an environmental point of view because the bitumen stored in the barrels must be reheated before use as a road binder. However, this operation is difficult to implement for this type of packaging and the drums are a 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 when transferring to the tanks of the production units of the mix. As for handling and transporting bituminous products in these drums, they may be difficult and dangerous if specialized drum handling equipment is not available at the carriers or where the bitumen is used.

As other examples of packaging, mention may be made of bitumen 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 easily manipulated. US 3,026,568 discloses bitumen granules coated with a powdery material, such as limestone powder. Nevertheless, this type of granular bitumen does not prevent the flow of bitumen, especially at high ambient temperature.

The application WO2009 / 153324 describes bitumen granules coated with a polymeric anti-caking compound, in particular polyethylene. The disadvantage of this coating is that it modifies the properties of the bitumen during its road application.

The application WO 2016/016318 describes bitumen granules comprising a chemical additive which may be a mono or a polyacid, a hydrazide, or a diamide. These bitumen granules allow the transport and / or storage and / or handling of the bitumen at room temperature without it flowing, as well as reducing their adhesion and agglomeration between them.

The application US 2011/0233105 describes solid asphalt at room temperature in the form of granules comprising a core and a coating layer. The core consists of recycled materials and asphalt binder. The coating layer may include one or more water-resistant polymers, wax, or fines. This The purpose of the coating layer is to prevent adhesion of the particles to each other, but also to adjacent surfaces during storage. This document does not disclose the content of viscosifying compound with respect to the total weight of the coating layer. It also does not disclose the viscosity of the compounds used in the composition of the coating layer.

FR 2 992 654 discloses bituminous compositions comprising a bitumen, a first additive comprising at least one fatty acid ester function and a second additive comprising at least one organogelling compound. These compositions have improved thermal susceptibility and can be used for road and industrial applications.

The Applicant has therefore sought to develop bitumens capable of being subjected to high ambient temperatures without flowing, in particular bitumens in the form of granules whose adhesion and agglomeration during their transport and / or storage and / or or handling at high ambient temperature is reduced compared to the granules of the prior art.

There is therefore a need to provide a bitumen composition transportable and / or storable and / or manipulable at room temperature, to overcome the disadvantages of the prior art.

An object of the present invention is to provide a bitumen composition transportable and / or storable and / or manipulable at high ambient temperature, and whose properties are preserved over time.

In particular, the object of the present invention is to provide a transportable and / or storable bitumen composition for a duration greater than 2 months, preferably 3 months, and at high ambient temperature, especially at a temperature below 100 ° C. preferably from 20 ° C to 80 ° C.

Another object of the invention is to provide an easily manipulable bitumen composition, especially at high ambient temperature, in particular at a temperature of up to 100 ° C, preferably from 20 ° C to 80 ° C.

In particular, the object of the present invention is to provide an easily manipulable bitumen composition after a duration of transport and / or prolonged storage at high ambient temperature, in particular during a transport and / or storage time greater than 2 months, preferably greater than 3 months, and at a temperature of up to 100 ° C, preferably between 20 ° C and 80 ° C. An object of the present invention is to provide a bitumen composition in a form that allows its flow in solid form at room temperature, so that it can be handled without loss of material. An attempt has been made to provide a bitumen composition which is in a form suitable for packaging it in packaging, deconditioning it, transferring it into equipment, even at a high ambient temperature, without having to heat it, and without loss. of matter. The proposed bitumen is in divided form and solid at room temperature so that it solves satisfactorily the problems mentioned above.

Another objective is to propose an industrial and economical process for producing a transportable and / or storable and / or manipulable bitumen composition at ambient temperature.

Another object of the invention is to provide an industrial and economical process for manufacturing asphalt from a transportable bitumen composition and / or storable and / or manipulable at room temperature.

Another objective of the invention is to propose an ecological and economical process for transporting and / or storing and / or handling a bitumen composition at ambient temperature, making it possible to avoid the use of additional means for maintaining said bitumen in temperature. during transport and / or storage and / or handling and to minimize the presence of waste and / or residues.

Summary of the invention

The invention relates to a room-temperature solid bitumen in the form of granules comprising a core and a coating layer in which:

the core comprises at least one bitumen base,

and

the coating layer comprises at least:

An oil chosen from a hydrocarbon oil of petroleum or synthetic origin,

At least one organogelling compound chosen from the compounds of general formula (I), (II) or (V):

in which Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group, and optionally substituted with one or more C 1 -C 6 alkyl groups; C20, and

R 1 represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions;

R ₂ - (NH) _n CONH- (X) _m - (NHCO) _p (NH) _n -R ₂ '(II) the groups R ₂ and R ₂ ', which may be identical or different, represent a saturated or unsaturated hydrocarbon chain, linear, branched or cyclic, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, hydrocarbon rings Cs-C ₂₄ and / or C ₄ hydrocarbon heterocycles -C ₂₄ comprising one or more heteroatoms such as N, O, S, and R ₂ 'can be H;

the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, hydrocarbon rings in Cs -C ₂₄ and / or C ₄ -C ₂₄ hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

n, m and p are integers having a value of 0 or 1 independently of one another;

R ₅ - (COOH) _z (V) R ₅ represents a linear or branched chain, saturated or unsaturated 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 .

According to a preferred embodiment, the hydrocarbon oil is chosen from hydrocarbon oils of petroleum origin.

According to a preferred variant, the hydrocarbon oil is chosen from aromatic oils having an aromatic content of between 30 and 95% by weight, advantageously between 50 and 95% by weight, more advantageously between 60 and 95% by weight. relative to the total mass of the aromatic oil.

According to another preferred variant, the hydrocarbon oil is chosen from paraffinic oils having a total content of paraffinic compounds of at least 50% by weight relative to the total mass of the paraffinic oil. Advantageously, according to this variant, the paraffmic oil has the respective contents:

(i) a total content of paraffinic compounds of between 50% and 90%;

(ϋ) a total content of naphthenic compounds of between 5% and 25%; and

(iii) a total content of aromatic compounds of between 5% and 25%, the percentages being expressed by weight relative to the total mass of the paraffmic oil.

According to a preferred embodiment, the coating layer comprises from 80% to 99.9% of at least one oil, by weight relative to the total mass of the coating layer.

According to a preferred embodiment, the coating layer comprises from 0.1 to 10%, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of organogelling compound. relative to the total mass of the coating layer. According to a preferred embodiment, the core further comprises at least one compound chosen from organogelling compounds.

According to another preferred embodiment, the core further comprises 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 the standard EN 1426 and that the TBA is measured according to the standard EN 1427. The invention also relates to a method of manufacturing a bitumen as described above and in a manner detailed below, this method comprising:

i) shaping the core from at least one bitumen base,

ii) coating the core on all or part of its surface with a coating composition,

iii) optionally, drying the granules obtained in step ii) at a temperature ranging from 20 to 60 ° C, for a period ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours.

The invention also relates to a bituminous mix which comprises a bitumen as described above and in detail below and which further comprises aggregates and optionally mineral and / or synthetic fillers.

According to a preferred embodiment, the bituminous mix is asphalt pavement, bituminous concrete, or bituminous mastic.

The invention also relates to a method of manufacturing asphalt mixes comprising at least one road binder and aggregates, the road binder being chosen from the bitumens described above and in detail below, this process comprising at least the steps of :

heating the aggregates at a temperature ranging from 100 ° C. to 180 ° C., preferably from 120 ° C. to 160 ° C., mixing the aggregates with the road binder in a tank such as a kneader or a kneading drum,

- Obtaining mixes. According to a preferred embodiment, the method does not include a heating step of the road binder before mixing with the aggregates.

The invention also relates to a method for transporting and / or storing bitumen, said bitumen being transported and / or stored as solid bitumen at room temperature as described above and in detail below.

detailed description

The objectives that the applicant has set for itself have been achieved through the development of bitumen compositions in a divided form, having a core / shell structure, in which the core is based on bitumen and the coating layer, with base of a gelled oily composition, and which gives the overall structure improved properties compared to bitumen granules known from the prior art.

"Ambient temperature" means the temperature resulting from the climatic conditions in which the road bitumen is transported and / or stored and / or handled. Specifically, the ambient temperature is equivalent to the temperature reached during transport and / or storage and / or handling of the road bitumen, it being understood that the ambient temperature implies that no heat input is provided other than that resulting climatic conditions.

The invention relates to bitumens capable of being subjected to a high ambient temperature, in particular a temperature of up to 100 ° C, preferably from 20 ° C to 80 ° C.

By "solid bitumen at ambient temperature" is meant a bitumen having a solid appearance at ambient temperature regardless of the conditions of transport and / or storage and / or handling. More specifically, solid bitumen at ambient temperature is understood to mean a bitumen that retains its solid appearance throughout transport and / or storage and / or handling at ambient temperature, that is to say a bitumen that does not not at room temperature under its own weight and more, which does not does not flow when subjected to pressure forces from transport and / or storage and / or handling conditions.

"Coating layer covering all part of the surface of the core" means that the coating layer covers at least 90% of the surface of the core, preferably at least 95% of the surface of the core, more preferably at least 99% of the surface of the heart.

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

By "softening point" is meant the so-called "ring ball 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 ball of standard diameter steel, after passing through the test material (glued in a ring), reaches the bottom of a standardized vessel filled with a liquid that is gradually heated, and in which the device has been immersed.

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

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

A first object of the invention relates to a solid bitumen at room temperature in the form of granules comprising a core and a coating layer covering all or part of the surface of the core in which:

the core comprises at least one bitumen base and, the coating layer comprises at least:

An oil chosen from a hydrocarbon oil of petroleum or synthetic origin, and

At least one organogelling compound.

- The bitumen base

Advantageously, the core or core of the solid bitumen granules according to the invention is prepared from a bitumen base, said core being prepared by putting in contact:

one or more bitumen bases, and

- optionally at least one organogelling compound,

possibly a pitch,

optionally at least one anti-caking compound.

For the purposes of the invention, the terms "bitumen" and "road bitumen" are used, in an equivalent manner and independently of one another. By "bitumen" or "road bitumen" is meant any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more additives. When said compositions are intended for a road application, they are more frequently referred to as "road bitumen". The invention also has applications in fields other than the road domain.

Among the bitumen bases that may be used according to the invention, mention may first be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. . The bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil. The bitumen bases may be chosen from bitumen bases or bitumen base mixtures derived from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches. The bitumen bases can be obtained by conventional processes for the manufacture of bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of the oil. These bitumen bases may optionally be visbroken and / or deasphalted and / or rectified in air. Vacuum distillation of atmospheric residues from atmospheric distillation of crude oil is common. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a vacuum distillation, the charge feeding the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a charge usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This method provides a base blown, or semi-blown or oxidized or rectified in air or rectified partially in air.

The various 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 bitumen base for recycling. The bitumen bases may be bitumen bases of hard grade or soft grade.

According to the invention, for the conventional processes for the production of bitumen bases, production temperatures of between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C., more preferably between 140 ° C. and 170 ° C, and 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 "manufacturing temperature" means the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by the standard NF EN 12594.

According to the invention, the blown bitumens can be manufactured in a blowing unit, by passing a stream of air and / or oxygen through a starting bituminous base. This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid. Generally, the blowing is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long periods of time typically between 30 minutes and 2 hours, continuously or in batches. The duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.

Preferably, the bitumen base used to manufacture the granules of the invention has a needle penetration measured at 25 ° C according to the EN 1426 standard of 5 to 330 1/10 mm, preferably 20 to 220 1 / 10 mm.

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

According to one embodiment of the invention, the bitumen base may also comprise at least one known bitumen elastomer such as copolymers SB (block copolymer of styrene and butadiene), SBS (styrene-butadiene-styrene block copolymer) , SIS (styrene-isoprene-styrene), SBS * (star styrene-butadiene-styrene block copolymer), SBR (styrene-b-butadiene rubber), EPDM (modified ethylene propylene diene). These elastomers may 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 permitting crosslinking without a crosslinking agent as described in documents WO2007 / 058994, WO2008 / 137394 and by the applicant in patent application WO2011 / 013073.

Advantageously, according to this embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises from 0.5% to 15% by weight, preferably from 1% to 15% by weight, more preferably of 2%. at 12% by weight of elastomer relative to the total mass of the bituminous core composition.

According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one olefinic polymer adjuvant.

Advantageously, according to this embodiment, the bituminous composition of which the core of the granules is composed comprises from 0.05% to 15% by weight, preferably from 0.1% to 10% by weight, more preferably from 0, 5% to 6% by weight of the olefinic polymer adjuvant relative to the total mass of said core.

According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one pitch.

Advantageously, according to this embodiment, the bituminous composition forming the core of the granules comprises from 2 to 30% by weight of pitch relative to the total mass of the composition, preferably from 3 to 20% by weight of pitch relative to the total mass of the bituminous composition forming the core of the granules. According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one anti-caking agent.

Advantageously, according to this embodiment, the composition forming the core of the bitumen granules comprises between 0.5% and 20% by weight, preferably between 2% and 20% by weight, more preferably between 4% and 15% by weight. mass of at least one anti-caking agent relative to the total mass of the bituminous composition forming the core of said granules.

According to one embodiment of the invention, the bituminous composition of which the core of the granules is composed comprises at least one organogelling compound.

Advantageously, according to this embodiment, the composition forming the core of the bitumen granules comprises from 0.1% to 10% by weight, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of organogelling compound relative to the total mass of the bituminous composition forming the core of said granules.

- olefin polymer adjuvant

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

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

The A monomer is selected from vinyl acetate and alkyl acrylates or methacrylates to C _6.

Monomer B is selected 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 weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.

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

Advantageously, the additive polymer is selected from olefinic random terpolymers of ethylene (b), of a monomer A chosen from acrylates or methacrylates of alkyl to C ₆ and a monomer B selected from acrylate 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 From 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.

- The pitch:

The bitumen base is chemically different from the pitch used. Therefore, the bitumen base and the pitch can not be used one to replace the other because their chemical characteristics are different. The pitch can be used as a mixture in the bitumen base.

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 the French dictionary, "pitch" is a residue of distillation of petroleum tars, coal tar, wood or other organic molecules.

The pitch used in the invention is chosen from petroleum distillation residues, also known as "petroleum pitch".

In the description, the terms "pitch" will be used independently of one another,

"Oil pitch" and "deasphalter pitch".

The pitches can be obtained by conventional refinery manufacturing processes. The manufacturing process corresponds to the succession of atmospheric distillation and vacuum distillation. In a first step, the crude oil is subjected to distillation at atmospheric pressure, which leads to the production of a gaseous phase, various distillates and an atmospheric distillate residue. Then, the residue of the atmospheric distillation is itself subjected to distillation under reduced pressure, called vacuum distillation, which makes it possible to separate a heavy gas oil, various sections of distillate and a distillation residue under vacuum. This vacuum distillation residue contains "petroleum pitch" in varying concentration.

It is possible to obtain "oil pitch" by two methods:

l ^st method:

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

2 ^nd process:

The vacuum distillation residue is subjected to a solvent extraction, and more precisely to furfural. 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 "oil pitch".

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

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

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

The mechanical properties of pitches are generally appreciated by determining a series of mechanical characteristics by standardized tests, the most used of which are needle penetration expressed in 1/10 mm and the softening point determined by the ball and ring test. , also called ball and ring softening temperature (TB A).

According to one embodiment of the invention, the pitch exhibits needle penetration at 25 ° C. of 0 to 1/10 mm, preferably 0 to 1/10 mm, more preferably 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 respectively having a softening point between 115 ° C and 125 ° C, between 135 and 145 ° C or between 165 and 175 ° C.

The addition of a pitch with the mechanical characteristics presented above in a bituminous composition making up the core of the granules of the invention makes it possible to improve the module properties of said bituminous composition and also to improve the properties of the modulus of the bituminous mixes. In addition, the addition of the pitch according to the invention in a bituminous composition comprising the core of the granules of the invention 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 with respect to a bituminous composition without pitch.

The bituminous composition constituting the core of the granules of the invention may be prepared by a process comprising at least the steps of:

· Heating of the bitumen base at a temperature ranging from 140 to 180 ° C,

• Introduction of pitch in the bitumen base,

• Agitation of the mixture at a temperature ranging from 140 to 180 ° C until a homogeneous mixture. It has been found that the pitch mixes perfectly with the bitumen base.

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

Advantageously, the pitch does not need to be heated, before being added to the bitumen base. Although the pitch usually has a melting temperature greater than 220 ° C, it solubilizes in bitumens at the usual temperatures of preparation of the bituminous compositions. The process for manufacturing the bituminous composition making up the core of the granules of the invention is easy to implement and does not require long-distance hot transporting the pitch intended to improve the properties of the bitumen base.

According to one embodiment of the invention, the pitch used in the process for producing the core of the granules is in cold solid form and divided, preferably in the form of granules. This form facilitates the handling of the pitch for its implementation in the manufacture of the bituminous composition comprising the core of the granules of the invention.

By cold solid pitch and in divided form is meant a solid pitch at room temperature which is packaged in a divided form, that is to say in the form of units distinct from each other, for example granules.

The pitch granules can have within the same population of granules, one or more forms chosen from a cylindrical, spherical or ovoid shape. More specifically, the pitch granules preferably have a cylindrical or spherical shape.

Advantageously, the size of the pitch granules is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 2 to 30 mm. For example, the use of a die makes it possible to control the manufacture of granules of a chosen size. Sieving allows the selection of granules according to their size.

To allow the formation of pitch granules which do not adhere to one another and resist compression during their storage, it may be advantageous to use pitch granules coated in whole or part of their surface by an anti-caking compound. . The pitch, in the form of granules optionally coated with an anti-caking compound, is easily handled after a period of transport and / or extended storage. The anti-caking compound is then found in the composition forming the heart of the granules.

- Anti-caking agent:

The anti-caking compound may be used as an additive in the composition of which the core of the granules is made.

The anti-caking compound may also be used as an additive in the coating composition.

It may also optionally be used to form a second coating layer on all or part of the surface of the granules.

The anti-caking compound is of mineral or organic origin.

More preferably, the anti-caking compound is chosen from: talc; the fines, also called "fillers", generally of diameter less than 125 μιη, such as fine silicones, with the exception of fine limestones; ultrafine; sand such as fountain sand; cement ; carbon; wood residues such as lignin, lignosulphonate, conifer needle powders, conifer cone powders, especially pine powders; the ashes of rice balls; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silicates, silicon hydroxides and other silicon oxides; silica fumes; plastic powder; lime; the plaster ; rubber crumb; polymer powder, such as styrene-butadiene copolymers (SB), styrene-butadiene-styrene copolymers (SB S) and mixtures of these materials.

Advantageously, the anti-caking compound is chosen from: fines, generally of diameter less than 125 μιη; silica fumes; wood residues such as lignin, conifer needle powders and conifer cone powders; their mixtures.

By way of example, the anti-caking agent may be chosen from silica fumes. Preferably, the anti-caking compound is chosen from silica fumes. In particular, when the composition comprising the core of the granules comprises at least one anti-caking compound, it is preferably chosen from silica fumes. When the granules according to the invention are coated, on all or part of their surface, with a coating layer comprising an anti-caking compound, said anti-caking compound is preferably chosen from silica fumes.

According to one embodiment, the core of the granules consists of a composition comprising at least one anti-caking agent, preferably selected from silica fumes, and the surface of said granules is covered, at least in part, with a coating layer comprising an anti-caking compound, preferably selected 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, in the sense of the invention can be used these compounds indifferently from one another

By "fumed silica" is meant either a fumed silica or a fumed silica derivative.

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 methods are generally referred to as pyrogenic processes whose overall reaction is: S1CI ₄ + H ₂ + O ₂ → SiO ₂ + 4 HCl.

Pyrogenic silicas are distinguished from other silicon dioxides in that they have an amorphous structure. High purity (> 99.8% silica), they have a low hydrophilic character (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 ² / g.

The specific surface area of the fumed silica defined in m ² / g commonly referred to as "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) (BET).

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 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 selected 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 that is miscible with water in all proportions.

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

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

silanized fumed silicas, as described in WO 2004/020532, or in

WO 2007/128636,

hydrophilic fumed 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.

When the surface of the granules is covered, at least in part, with a coating layer comprising a fumed silica compound, said fumed silica compound can then 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 in dispersion in a solvent which evaporates after application. Preferably, when the coating composition comprises at least one pyrogenic silica compound and at least one solvent, the composition comprises from 5 to 70% by weight of fumed silica compound relative to the total weight of the coating 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.

The silica fume used in the invention are commercially available and for example can be sold by Evonik Degussa under the trademark Aerosil ^® such as AEROSIL ^® 200, by Cabot Corporation under the trademark CAB-O-SIL ^® and CAB -O-SPERSE ^® or Wacker Chemie AG under the brand name HDK ^® .

- The composition forming the heart of the granules:

The composition forming the heart of the granules comprises:

one or more bitumen bases, and

- optionally at least one organogelling compound,

- possibly a pitch.

Optionally, it may also include:

one or more additives selected from elastomers, olefinic polymer adjuvants, anti-caking compounds.

Advantageously, the composition forming the core of the granules, comprising a bitumen base additive with at least one organogelling compound and / or at least one pitch, has a target penetrability ranging from 5 to 45 l / 10 mm and / or a ball softening temperature and target ring (TBA) greater than or equal to 90 ° C, provided that penetrability is measured at 25 ° C according to EN 1426 and TBA according to EN 1427.

These characteristics are achieved by methods known to those skilled in the art, by hot mixing the one or more components in the bitumen base in the appropriate amounts as indicated above for each category of component. The temperature of the bitumen base during the introduction of the additives is chosen according to their nature, in order to avoid their degradation. The stirring is more or less vigorous and more or less prolonged, in order to obtain a homogeneous composition without degrading the properties of the composition forming the heart of the granules. The composition thus obtained is directly used in the process of manufacturing bitumen granules with core / envelope structure described below.

Advantageously, the bituminous composition forming the core of the granules comprises:

one or more bitumen bases,

between 0, 1% and 5% by weight, preferably between 0.5% and 4% by weight, more preferably between 0.5% and 2.5% by weight of at least one organogelling compound, relative to to the total mass of bitumen of said granules. Advantageously, the bituminous composition forming the core of the granules comprises:

one or more bitumen bases,

between 0, 1% and 5% by weight, preferably between 0.5% and 4% by weight, more preferably between 0.5% and 2.5% by weight of at least one organogelling compound relative to the mass total amount of bitumen of said granules, and between 0.5% and 20% by weight, preferably between 2% and 20% by weight, more preferably between 4% and 15% by weight of at least one anti-agglomerating compound. relative to the total mass of bitumen of said granules.

- The oil:

Preferably the oil is a hydrocarbon oil of petroleum origin. It can be aromatic or paraffinic type.

According to one embodiment, the oil is composed of 90 to 100% by weight of at least one hydrocarbon oil of petroleum origin, advantageously from 95 to 100%, more preferably from 98 to 100% by weight of at least a hydrocarbon oil of petroleum origin. Even more advantageously, the oil consists of a hydrocarbon oil of petroleum origin or a mixture of hydrocarbon oils of petroleum origin.

In a preferred embodiment of the invention, the hydrocarbon oil of petroleum origin is chosen from aromatic oils. More preferably, the aromatic oils have a content of aromatic compounds of between 30 and 95% by weight, advantageously between 50 and 95% by weight, more advantageously between 60 and 95% by weight relative to the total mass of the aromatic oil (SARA method: Saturated / Aromatic / Resins / Asphaltenes).

More preferably, the aromatic oils have a content of saturated compounds of between 1 and 20% by weight, advantageously between 3 and 15% by weight, more preferably between 5 and 10% by weight (SARA method: Saturated / Aromatic / Resins Asphaltenes).

More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by weight, advantageously between 3 and 5% by weight, (SARA method: Saturated / Aromatic / Resins / Asphaltenes). The contents of saturated compounds, resins and aromatics mentioned in the present application are determined according to ASTM D2140, in% by weight relative to the mass of the oil.

More preferably, the aromatic oils have a kinematic viscosity at 100 ° C of between 0.1 and 150 mm ² / s, advantageously between 5 and 120 mm ² / s, more advantageously between 7 and 90 mm ² / s (Method ASTM D 445).

More preferably, the aromatic oils have a Cleveland flash point greater than or equal to 150 ° C., advantageously between 150 ° C. and 600 ° C., more advantageously between 200 ° C. and 400 ° C. (EN ISO 2592 method).

More preferably, the aromatic oils have an aniline point between 20 ^° C and 120 ^° C, preferably between 40 ^° C and 120 ^° C (ASTM Method: D61 1).

More preferably, the aromatic oils have a density at 15 C of between 400 kg / m ³ and 1500 kg / m ^3, preferably between 600 kg / m ³ and 1200 kg / m ^" ', more preferably between 800 kg / m ³ and 1000 kg / m ^"(ethod ASTM D4052). According to this advantageous embodiment, the aromatic oil comprises aromatic extracts of petroleum residues obtained by extraction or dearomatization of residues of distillations of petroleum fractions. The aromatic extracts are secondary products of the process of refining crude oils, obtained especially from the products of the vacuum distillation of atmospheric residues. They result from a single or double extraction of the raffinate that can be used in lubricants by means of a polar solvent.

The different extracts are classified in different categories according to their process of obtaining and are the following ones:

- DAE (Distillate Aromatic Extract in English, or distillate aromatic extract)

- MES (Mild Extract Solvate in English or gentle extraction solvent), - TEDA (Treated Distillate Aromatic Extract in English or aromatic distilled extract treated),

- RAE (Residual Aromatic Extract in English or residual aromatic extract),

- TREE (Treated Residual Aromatic Extract in English or residual aromatic extract treated)

For example, the aromatic oils that can be used according to the invention can be chosen from the following products sold by TOTAL under the names Plaxolene 50® (also sold under the trade name Regenis 50®), Plaxolene TD346® and Plaxolene MSI 32®. .

The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the aromatic oil and the refining process used.

According to one embodiment, the oil is composed of 90 to 100% by weight of at least one oil of aromatic petroleum origin and from 0 to 10% by weight of one or more other oils.

For example, Regenis 50 ® is an RAE (Residual Aromatic Extract) that presents:

a density at 15 ° C between 980 kg / m ³ and 1010 kg / nr (method AS! VI 1) 4052).

a flash point (Cleveland) of approximately 230 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C between 60 and 85 mm ² / s (Method

ASTM D 445),

an aniline point between 53 and 65 ° C. (ASTM D611 method). For example, Plaxolene TD346 ® is a TDAE (Treated Distillates Aromatic Extract) that presents:

a density at 15 ° C of between 940 kg / m ³ and 970 kg / m ³ (ASTM Method D4052),

- a flash point (Cleveland) of about 220 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C of between 16 and 23 mm ² / s (ASTM Method D 445),

an aniline point between 64 and 72 ° C. (ASTM D611 method).

For example, Plaxolene MSI 32 ® is a MES (Mild Extract Solvate) that presents:

- a density at 15 ° C between 895 kg / m ³ and 925 kg / m ³ (Method

ASTM D4052),

- a flash point (Cleveland) of about 230 ° C (EN ISO 2592 method),

a kinematic viscosity at 100 ° C of between 13 and 17 mm ² / s (ASTM Method D 445),

an aniline point between 85 and 100 ° C. (ASTM D611 method).

According to a second advantageous embodiment, the oil is a paraffinic oil comprising mainly paraffinic extracts of petroleum residues. According to this specific embodiment, advantageously, the oil comprises a total content of paraffinic compounds of at least 50% by weight, preferably at least 60% by weight, for example between 50% and 90%. >, preferably between 60%> and 90%>, more preferably between 50% and 80% and in particular between 55% and 70%, or in particular between 60%> and 75%.

In a more specific embodiment, the oil also contains a total content of naphthenic compounds which does not exceed 25%, for example between 5% and 25%, and in particular between 10% and 25%. %.

In a more specific embodiment, the oil also contains a total aromatic content which does not exceed 25%, for example between 5% and 25%, and in particular between 8% and 18%.

In a particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 50% and 90%; (ii) a total content of naphthenic compounds of between 5% and 25%; and

(iii) a total content of aromatic compounds of between 5% and 25%. In a more particularly preferred embodiment, the oil is a paraffinic oil, comprising the respective contents:

(i) a total content of paraffinic compounds of between 60% and 75%;

(ii) a total content of naphthenic compounds of between 5% and 25%; and

(iii) a total content of aromatic compounds of between 5% and 25%. In a still preferred embodiment, the oil is a paraffinic oil DAO, comprising the respective contents:

(i) a total content of paraffinic compounds of between 60% and 75%;

(ii) a total content of naphthenic compounds of between 15% and 25%; and

(iii) a total content of aromatic compounds of between 10% and 15%.

In a preferred embodiment of the invention, the paraffmic oils are derived from distillation deasphalting cuts under reduced pressure (vacuum residue, RSV) crude oil (hereinafter referred to as "DAO oil"). The principle of deasphalting is based on a separation by precipitation of a petroleum residue in two phases: i) a phase called "deasphalted oil", also called "oil matrix" or "oil phase" or DAO (DeAsphalted Oil in English); and ii) a phase called "asphalt". Oils corresponding to the characteristics below and usable according to the invention are obtained by vacuum residue deasphalting processes (RSV) from petroleum refining, for example by deasphalting with a C 3 solvent. C6, preferably with propane. Deasphalting processes are well known to those skilled in the art and are described for example in FR3014111, US 2004/0069685, US 4,305,812 and US 4,455,216 or in Lee et al., 2014, Fuel Processing Technology 119: 204-210.

In Lee et al., 2014, Fuel Processing Technology 119: 204-210, residues from vacuum distillation (RSV) are separated according to their molecular weight in the presence of C3 to C6 solvent (eg propane). The so-called DAO oil thus obtained is rich in paraffin, has a very low content of asphaltenes, has a temperature of evaporation between 440 ° C and 750 ° C, and API gravity much higher than that of vacuum residues.

The API gravity or API gravity of an oil (API gravity) can be obtained from the following formula (1):

with:

- G _API , the API gravity of the oil considered (expressed without unit), and

- d, the density at 16 ° C (60 ° F) of the oil in question (expressed without unit) taking water as a reference.

The respective contents of paraffinic, naphthenic and aromatic compounds depend to some extent on the nature of the crude oil at the origin of the DAO oil and the refining process used. Those skilled in the art can determine the respective contents of paraffinic, naphthenic and aromatic compounds of a DAO oil for example using the SARA fractionation method also described in Lee et al., 2014, Fuel Processing Technology 119: 204-210 and thus selecting the appropriate DAO oil for the preparation of the gelled oil composition according to the invention. The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the ASTM D2140 standard, in% by weight relative to the mass of the oil.

According to an advantageous embodiment, the oil is composed of a mixture based on an aromatic hydrocarbon oil and a paraffinic oil. According to an advantageous embodiment, the oil is composed of 90 to 100% by weight of at least one aromatic oil, preferably an RAE oil, and from 0 to 10% by weight of one or more other oils.

According to an advantageous embodiment, the oil is composed of 90 to 100% by weight of at least one paraffinic oil, preferably a DAO oil, and from 0 to 10% by weight of one or more other oils. Preferably, the oil is a paraffinic oil, preferably a DAO paraffinic oil.

The other oils used can be chosen from oils of petroleum origin, oils of vegetable origin and their mixtures. For example, vegetable oils can be chosen from rapeseed, sunflower, soybean, flax, olive, palm, castor oil, wood, corn, squash, grape seed oil. , jojoba, sesame, walnut, hazelnut, almond, shea, macadamia, cotton, alfalfa, rye, safflower, peanut, coconut and copra, and mixtures thereof. The organogelling compound

The coating layer of solid bitumen at ambient temperature in the form of granules according to the invention comprises at least one organogelling compound.

The heart of the solid bitumen at ambient temperature in the form of granules according to the invention may also comprise at least one organogelling compound.

In particular, the coating layer comprises at least one organogelling compound in an amount adapted for this composition to form a solid coating at room temperature.

Preferably, the composition forming the heart of the solid bitumen granules at ambient temperature comprises at least one organogelling compound in an amount adapted so that this composition is solid at room temperature and in divided form.

In one embodiment of the invention, the organogelator is an organic compound. Advantageously, the organogelling compound has a molar mass of less than or equal to 2000 gmol ^-1 , preferably a molar mass less than or equal to 1000 gmol ^-1 .

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

in which :

Ar 1 and Ar 2 represent, independently of one another, a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group and optionally substituted by one or more C1-C20 alkyl groups, and

R 1 represents an optionally substituted divalent radical, the main chain of which comprises from 6 to 20 carbon atoms and at least one group chosen from amide, ester, hydrazide, urea, carbamate and anhydride functions.

Ar 1 and / or Ar 2 are preferably substituted with at least one alkyl group of 1 to 10 carbon atoms, advantageously at one or more ortho positions with respect to the hydroxyl group (s), more preferably Ar 1 and Ar 2 are 3,5-dialkyl-4-hydroxyphenyl groups, advantageously 3,5-di-tert-butyl-4-hydroxyphenyl groups.

Preferably, R 1 is in the para position with respect to a hydroxyl group of Ar 1 and / or Ar 2.

An example of a compound of formula (I) is 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.

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

R ₂ - (NH) _n CONH- (X) _m - (NHCO) _p (NH) _n -R ₂ '(II),

in which,

the groups R ₂ and R ₂ ', which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, optionally substituted by one or more hydroxyl groups or amino groups, and optionally comprising heteroatoms such as N, O, S, Cs-C ₂₄ hydrocarbon rings and / or C ₄ -C ₂₄ hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S and R ₂ 'may be H;

the group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms such as N, O, S, Cs-hydrocarbon rings; C ₂₄ and / or C ₄ -C ₂₄ hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

n, m and p are integers having a value of 0 or 1 independently of one another. According to this variant, when the integer ma has a value of 0 and when the integer pa has a value of 1, then the groups R ₂ - (NH) _n CONH and NHCO (NH) _n -R ₂ 'are covalently linked. and together form a CONH-NHCO hydrazide bond. The group R ₂ , or the group R ₂ ', then represents 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 condensed polycyclic system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms.

Still according to this variant, when the integer ma has a value of 1, then the group R ₂ , the group R ₂ 'and / or the group X represents at least one group chosen from: a hydrocarbon chain of at least 4 atoms carbon, an aliphatic ring of 3 to 8 atoms, an aliphatic condensed polycyclic system, partially aromatic or wholly aromatic, each ring comprising 5 or 6 atoms.

Preferably, the group R ₂ and / or R ₂ 'represents an aliphatic hydrocarbon chain of 4 to 22 carbon atoms, in particular, chosen from the groups C 4 H 9, C 5 H 11, C 9 H 19, C 11 H 23, C 12 H 25, C 17 H 35, C 18 H 37, C 21 H 43, C 22 H 45.

According to a first preferred embodiment, the group X represents a linear, saturated hydrocarbon-based chain comprising from 1 to 22 carbon atoms, advantageously from 1 to 12 carbon atoms, more preferably from 1 to 10 carbon atoms. Preferably, the group X is chosen from C ₂ H ₄ and C ₃ H _{6 groups} .

According to a second preferred embodiment, the group X can also be a cyclohexyl group or a phenyl group, the radicals R ₂ - (NH) _n CONH- and - NHCO (NH) _n -R ₂ 'can then be in the ortho position. , meta or para. Moreover, the radicals R ₂ - (NH) _n CONH- and -NHCO (NH) _n -R ₂ 'may be in the cis or trans position with respect to each other. In addition, when the radical X is cyclic, this ring may be substituted by groups other than the two main groups R ₂ - (NH) _n CONH- and -NHCO (NH) _n -R ₂ '.

According to a third preferred embodiment, the X group represents two cycles of 6 carbons, optionally substituted, connected by a CH ₂ group, these rings being aliphatic or aromatic. In this case, the group X is for example

Advantageously, according to this variant, the organogelling compound is a compound of general formula (II) chosen from hydrazide derivatives such as compounds C ₅ H "-CONH-NHCO-C ₅ Hn, C ₉ H 19 -C CONH-NHCO-C ₉ H 19, CnH ₂₃ -CONH-NHCO-C n H ₂₃ , C ₇ H ₃₅ -CONH-NHCO-C ₁₇ H ₃₅ , or C ₂ H ₄₃ -CONH-NHCO-C ₂ H ₄₃ ; diamides such as N, N'-ethylenediamine (laurylamide) of formula C n H ₂₃ -CONH-CH ₂ - CH ₂ -NHCO-C n H i _3, N, N ^* -éthylènedi (myristylamide) of the formula Ci ₃ H ₂₇ - CONH- CH ₂ -CH ₂ -NHCO-Ci ₃ H _27, N, N ^* -éthylènedi (palmitamide) of the formula H ₃ Ci ₅ i-CONH- CH ₂ -CH ₂ -NHCO-Ci ₅ H ₃ i, the N, ^NO -éthylènedi (stearamide) of the formula Ci ₇ H ₃₅ -CONH-CH ₂ -CH ₂ -NHCO-Ci ₇ H _35; and ureide derivatives such as 4,4'-bis (dodecylaminocarbonylamino) diphenylmethane of formula Ci ₂ H ₂ 5 -NHCONH-C ₆ H ₄ -CH ₂ -C ₆ H ₄ -NHCONH-Cl ₂ H 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 ₂ , X and R ₂ '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 ₂ and R ₂ 'is greater than or equal to 10, advantageously greater 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 ₂ -CONH- (X) _m -NHCO-R ₂ '(IIA)

wherein R ₂ , R ₂ ', m and X have the same definition as above.

Preferably, in the formula (IIA) when m = 1, the group X represents a saturated linear hydrocarbon-based chain containing from 1 to 22 carbon atoms, advantageously X represents a linear hydrocarbon-based saturated chain comprising from 1 to 12 carbon atoms more preferably from 1 to 4 carbon atoms. Preferably, the X group is chosen from C ₂ H and C ₃ H _{6 groups} . 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 ₂ , X and R ₂ '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 ₂ and R ₂ 'is greater than or equal to 10, advantageously greater 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 compounds C5H11-CONH-NHCO-C5H11, C9H19-CONH-NHCO-C9H19, C11H23-CONH-NHCO-C11H23, Ci ₇ H ₃₅ -CONH-NHCO-C ₁₇ H ₃₅ , or C ₂₁ H ₄₃ -CONH-NHCO-C21H ₄₃ ; diamides such as Ν, Ν'-ethylenedi (laurylamide) of formula C n H ₂₃ -CONH-CH 2 -CH 2 -NHCO-C 1 H ₃ i, Ν, Ν'-ethylenedi (myristylamide) of formula Ci ₃ H ₂₇ -CONH -CH2-CH2-NHCO-Ci ₃ H _27, N, N ^* -éthylènedi (palmitamide) of the formula H ₃ Ci ₅ i-CONH-CH ₂ -CH ₂ -NHCO-Ci ₅ H ₃ i N, N ^* -éthylènedi (stearamide) of the formula Ci ₇ H ₃₅ -CONH-CH ₂ -CH ₂ -NHCO-Ci ₇ H _35; monoamides such as laurylamide of formula CnH ₂₃ -CONH ₂ , myristylamide of formula Ci ₃ H ₂₇ -CONH ₂ , palmitamide of formula C ₅ H ₃ i-CONH ₂ , stearamide of formula C ₇ H ₃₅ -CONH ₂ .

Even more advantageously, the compound of general formula (IIA) is Ν, Ν'-ethylenedi (stearamide) of formula C ₇ H ₃₅ -CONH-CH ₂ -CH ₂ -NHCO-C ₁₇ H ₃₅ .

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

wherein R2 and R ₂ 'have the same definition as above.

Advantageously, according to this variant, the sum of the numbers of the carbon atoms of R2 and R ₂ '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 R2 is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14, and R ₂ '= H.

Advantageously, the compound of general formula (II) is chosen from hydrazide derivatives such as compounds C ₅ H ₅ -CONH-NHCO-C ₅ H _1, C ₉ H 19 -C CONH-NHCO- C9H19, C11H23-CONH-NHCO-C11H23, CIVHBS-CONH-NHCO-CIVHBS OR C21H43- CONH-NHCO-C ₂ H _43; diamides such as N, N'-ethylenedi (laurylamide) of formula C n H ₂₃ -CONH-CH ₂ -CH ₂ -NHCO-C 1 H ₃ i, N, N * -ethylenedi (myristylamide) of formula Ci ₃ H ₂ 7-CONH-CH ₂ -CH ₂ -NHCO-Cl ₃ H 27, N, N -ethylenedi (palmitamide) of formula Ci ₅ H ₃ i-CONH-CH ₂ -CH ₂ -NHCO-Ci ₅ H ₃ i, NB N, N-ethylenedi (stearamide) of the formula C ₇ H ₃₅ -CONH-CH ₂ -CH ₂ -NHCO-C ₁₇ H ₃₅ ; monoamides such as laurylamide of formula CnH ₂₃ -CONH ₂ , myristylamide of formula Ci ₃ H ₂₇ -CONH ₂ , palmitamide of formula Ci ₅ H ₃ i-CONH ₂ , stearamide of formula Ci ₇ H ₃₅ -CONH ₂ .

Even more advantageously, the compound of general formula (II) is Ν, Ν'-ethylenedi (stearamide) of formula C ₇ H ₃₅ -CONH-CH ₂ -CH ₂ -NHCO-C ₁₇ H ₃₅ .

Preferably, when the chemical additive is chosen from the organic compounds of formula (II), it is used in combination with at least one other chemical additive chosen from the organic compounds of formula (I), (III), (V) , (VI) and (VII) and / or the reaction products of at least one polyol C ₃ -C ₂ and at least one aldehyde C ₂ -C _12, in particular those comprising a group of formula (IV ).

According to a third variant, the organogelling compound is a compound of formula (III):

(R-NHCO) _X -Z- (NHCO-R ') _Y (III),

in which,

R and R ', which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, which may be optionally substituted, and optionally comprising heteroatoms such as N, O, S, rings; hydrocarbon, C ₅ -C ₂₄ and / or hydrocarbon monocyclic C ₄ - C ₂₄ comprising one or more heteroatoms such as N, O, S,

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

x and y are different integers with values ranging from 0 to 3 and such that x + y = 3. Preferably, when x is 0 and Z is Z ₂ , the compound of formula (III) is N 2, N 4, N 6 -tridecylmelamine having the following formula with R 'representing the group C ₉ H ₁₉ :

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

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

with R selected from the following groups, taken alone or in mixtures:

Other preferred compounds corresponding to formula (III) are such that: y is 0, Z represents Z ₁ and R represents a linear saturated hydrocarbon-based chain of 1 to 22 carbon atoms, preferably 8 to 12 carbon atoms. carbon atoms. According to a fourth variant, the organogelator compound is a reaction product of at least one polyol C3-C ₁₂ and at least one aldehyde C ₂ -C _12. Among the polyols that may be used, mention may be made of sorbitol, xylitol, mannitol and / or ribitol. Preferably, the polyol is sorbitol.

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

(IV)

with:

- x is an integer,

- R is selected from alkyl radical -C ₂ -alkenyl, C ₂ -C ₁₂ aryl, C ₆ - C ₁₂ aralkyl or C ₇ -C _12, optionally substituted by one or more halogen atoms, one or more C ₁ -C ₆ alkoxy groups

According to this variant, the organogelling compound is advantageously a sorbitol derivative. By "sorbitol derivative" is meant any reaction product, obtained from sorbitol. In particular, any reaction product obtained by reacting an aldehyde with D-sorbitol. This condensation reaction produces sorbitol acetals, which are derivatives of sorbitol. 1,3: 2,4-Di-O-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:

The sorbitol derivatives may thus be all the condensation products of aldehydes, especially aromatic aldehydes with sorbitol. Sorbitol derivatives of general formula will then be obtained:

where Ari and Ar ₂ 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, 1,3,3,4,5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono-O-benzylidene-D-sorbitol, 1,3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4-bis (3,4-bis), dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3,2,4-bis (p-propylbenzylidene) sorbitol, 1,3,2,4-bis (p-butylbenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxylbenzylidene) sorbitol, 1,3,2,4-bis (p-chlorobenzylidene) sorbitol, 1,3,2,4-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- (4) -methylbenzylidene) - D-sorbitol, 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol. Preferably, according to this variant, the organogelling compound is 1,3,3,4-Di-O-benzylidene-D-sorbitol.

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

R ₅ - (COOH) _z (V),

in which R ₅ 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 at 4.

Preferably, the group R ₅ is a saturated linear chain of formula C _w H _2w with w an integer ranging from 4 to 22, preferably from 4 to 12.

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

Preferably, according to this variant, the diacids (V) have the general formula

HOOC-C _w H _2w -COOH with w an integer ranging from 4 to 22, preferably from 4 to 12.

Advantageously, according to this variant, the organogelling 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 acid 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 organogelling compound is sebacic acid or acid

1,10-decanedioic with w = 8.

The diacids may 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 (reaction of Diels Aid for example).

Preferably, only one type of unsaturated fatty acid is dimerized. They derive, in particular, from the dimerization of an unsaturated fatty acid, in particular C ₈ to C 34, especially C ₁₂ to C ₂₂ , in particular C ₁₆ to C 20, and more particularly C ₁₈ . A preferred fatty acid dimer is obtained by dimerization of linoleic acid, which can then be partially or fully hydrogenated.

Another preferred fatty acid dimer has the formula HOOC- (CH ₂ ) 7 -CH = CH- (CH ₂ ) 7 -COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. In the same way, it is possible to find triacids of fatty acids and tetracides of fatty acids, obtained respectively by trimerization and tetramerization of at least one fatty acid.

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

or a group chosen from: H, - (CH ₂ ) q-CH ₃ , - (CH ₂ ) q -NH ₂ , - (CH ₂ ) q -OH, - (CH ₂ ) q-COOH or 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 organogelling compounds of formula (VI), there may be mentioned the following compounds:

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

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

R-NH-CO-CO-NH-R '(VII)

in which R and R ', which may be identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising heteroatoms, such as N, O, S, C5-C24 hydrocarbon rings and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S.

It will not be departing from the scope of the invention by combining several different chemical additives such as various organogelling compounds of formula (I), (II),

(III), (V), (VI) and (VII), the reaction products of at least one C3-C12 polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula

(IV), in the oil composition. Advantageously, the coating composition comprises at least one organogelling additive chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V).

More preferably, the coating composition comprises at least one organogelling additive selected from compounds of formula (I) or compounds of formula (V).

Preferably, the coating composition comprises at least one organogelling additive which is 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide.

According to an advantageous embodiment, the coating composition comprises at least two organogelling compounds.

According to a first variant of this embodiment, the coating composition comprises at least one first organogelling compound of formula (V) and at least one second organogelling compound chosen from: organogelling compounds of formula (I); organogelling compounds of formula (II); organogelling compounds of formula (III); organogelling compounds of formula

(V); organogelling compounds of formula (VI); the organogelling compounds of formula (VII) and the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), the second organogelling compound being distinct from the first organogelling compound.

Preferably, and according to this first variant, the coating composition comprises at least one first organogelling compound of formula (V) and at least one second organogelling compound chosen from: organogelling compounds of formula (I) and organogelling compounds of formula (I) II). When the second organogelling compound is chosen from organogelling compounds of formula (II), it is preferably chosen from organogelling compounds of formula (IIA).

Preferably, and still according to this first variant, the first organogelling compound 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 organogelling compound 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, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

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

According to a second variant of this embodiment, the coating composition comprises at least one first organogelling compound of formula (II) and at least one second organogelling compound chosen from: organogelling compounds of formula (I); organogelling compounds of formula (II); organogelling compounds of formula (III); organogelling compounds of formula (V); organogelling compounds of formula (VI); the organogelling compounds of formula (VII) and the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), second organogelling compound being distinct from the first organogelling compound.

Preferably, and according to this second variant, the first organogelling compound of formula (II) is chosen from organogelling compounds of formula (IIA).

More preferably, and according to this second variant, the coating composition comprises at least one first organogelling compound of formula (IIA) and at least one second organogelling compound chosen from: organogelling compounds of formula (I); organogelling compounds of formula (IIB); organogelling compounds of formula (III); organogelling compounds of formula (V); organogelling compounds (VI); organogelling compounds of formula (VII) and the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), the second organogelling compound being distinct from the first organogelling compound.

Even more preferentially, and according to this second variant, the coating composition comprises at least one first organogelling compound of formula (IIA) and at least one second organogelling compound chosen from: organogelling compounds of formula (I) and organogelling compounds of formula (V).

Preferably, and according to this second variant, the first organogelling compound of formula (II) is N, N'-ethylenedi (stearamide).

When the second organogelling compound is chosen from organogelling compounds of formula (V), it is preferably 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.

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

According to a fourth variant of this embodiment, the coating composition comprises at least one first organogelling compound of formula (I) and at least one second organogelling compound chosen from: organogelling compounds of formula (I); organogelling compounds of formula (II); organogelling compounds of formula (III); organogelling compounds of formula (V); organogelling compounds of formula (VI); the organogelling compounds of formula (VII) and the reaction products of at least one C ₃ -C ₁₂ polyol and at least one C ₂ -C ₁₂ aldehyde, in particular those comprising a group of formula (IV), the second organogelling compound being distinct from the first organogelling compound.

Preferably, and according to this fourth variant, the second organogelling compound is chosen from the organogelling compounds of formula (II) and the organogelling compounds of formula (V). Preferably, and according to this fourth variant, when the second organogelling compound is chosen from the organogelling compounds of formula (II), it is chosen from the organogelling compounds of formula (II A).

More preferably, and according to this fourth variant, the second organogelling compound of formula (II) is N, N'-ethylenedi (stearamide).

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

Even more preferentially, and still according to this fourth variant, the second organogelling compound 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, 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

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

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

Preferably, and according to this embodiment, the mass ratio of the first organogelling compound with respect to the second organogelling compound is from 1: 99 to 99: 1, preferably from 1: 9 to 9: 1, even more preferably from 1: 5 to 5: 1.

Advantageously, the coating composition comprises from 0.1% to 10% by weight, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of organogelling compound relative to to the total mass of the composition.

Advantageously, the core composition comprises at least one organogelling compound chosen from the organogelling compounds of formula (I), the organogelling compounds of formula (II) and the organogelling compounds of formula (V). More preferably, the core composition comprises at least one organogelling compound chosen from the organogelling compounds of formula (I) and the organogelling compounds of formula (V).

Preferably, the core composition comprises at least one organogelling compound which is sebacic acid.

Coating composition

The terms "coating composition" and "coating composition" are used interchangeably in the description.

Advantageously, the coating composition comprises at least one organogelling compound.

More preferably, the coating composition comprises at least one organogelling compound chosen from the compounds of formula (I), the compounds of formula (II) and the compounds of formula (V). Even more advantageously, the coating composition comprises at least one organogelling compound chosen from the compounds of formula (I) and the compounds of formula (V).

Preferably, the coating composition comprises at least one organogelling additive chosen from:

2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl)] propionhydrazide,

• sebacic acid,

and

• mixtures of these compounds.

Advantageously, the coating composition comprises from 0.1% to 10% by weight, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5% by weight of an organogelling compound. relative to the total mass of the coating composition.

Advantageously, when the organogelling compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, the coating composition comprises from 0.1% to 5% by weight, preferably from 0.2% to 3.5% by weight of organogelling compound relative to the total weight of the coating composition. The coating composition comprises the oil, the organogelling compound (s) and, if appropriate, other additives. The other additives may be chosen for example from: anti-caking compounds, adhesivity dopes, elastomers for bitumen, etc.

Advantageously, the coating composition comprises, or is essentially composed of:

80% to 99.9% by weight of at least one oil chosen from: hydrocarbon oils of petroleum or synthetic origin, advantageously from hydrocarbon oils of petroleum origin,

0.1% to 10% by weight, of at least one organogelling compound,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition.

Preferably, the coating composition comprises, or is essentially composed of:

85% to 99.8% by weight of at least one oil, chosen from: hydrocarbon oils of petroleum or synthetic origin, advantageously from hydrocarbon oils of petroleum origin,

0.2% to 5% by weight, of at least one organogelling compound,

· 0% to 10% by weight of one or more other additives,

relative to the total mass of the composition.

More preferably, the coating composition comprises, or is essentially composed of:

86.5% to 99.5% by weight of at least one oil chosen from: hydrocarbon oils of petroleum or synthetic origin, advantageously from hydrocarbon oils of petroleum origin,

0.5% to 3.5% by weight of at least one organogelling compound,

• 0% to 10% by weight of one or more other additives relative to the total mass of the composition. According to a first preferred embodiment, the organogelling compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl]] propionyl)] propionohydrazide:

Advantageously according to this embodiment, the coating composition comprises, or is essentially composed of:

85% to 99.9% by weight of at least one hydrocarbon oil of petroleum origin,

0.1% to 5% by weight of at least one organogelling compound of formula (I), advantageously 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] ] propionyl)] propionohydrazide,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition.

Preferably, the coating composition comprises, or is essentially composed of:

86.5% to 99.8% by weight of at least one hydrocarbon oil of petroleum origin,

0.2% to 3.5% by weight of at least one organogelling compound of formula (I), advantageously 2 ', 3-bis [(3- [3,5-di-tert-butyl] -4 hydroxyphenylpropionyl) propionohydrazide,

0% to 10% by weight of one or more other additives,

relative to the total mass of the composition. - Process for the preparation of the coating composition

The coating compositions may be prepared for example according to the following process comprising the steps of: a) mixing the oil, for example the oil DAO or RAE, and heating at a temperature of between 140 and 200 ° C., preferably between 150 and 180 ° C, for example from 1 minute to 30 minutes, addition of the organogelling compound, mixing and heating at a temperature of between 140 and 200 ° C., preferably between 150 and 170 ° C., for example from 10 minutes to 2 hours,

c) optionally adding one or more other additives, mixing and heating at a temperature between 140 and 200 ° C, preferably between 150 and 170 ° C, for example, from 5 minutes to 20 minutes,

use in the process of making granules.

The order of steps (a) to (c) can be changed.

- Production process of the granules:

Another object of the invention relates to a method for manufacturing a solid bitumen at room temperature in the form of granules composed of a core and a core coating layer, this method comprising:

i) shaping the core from at least one bitumen base,

ii) coating the core on all or part of its surface with a coating composition,

iii) optionally, drying the granules obtained in step ii) at a temperature ranging from 20 to 60 ° C, for a time ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours,

iv) optionally, coating the granules from step ii) or step iii), over all or part of their surface, with at least one anti-caking compound.

Preferably, the step ii) of application is by soaking, spraying, coextrusion, etc.

Preferably, step iv) of coating the granules is by dusting, sieving, etc. The shaping of the core of the granules from an optionally additive bitumen base can be carried out according to any known method, for example according to the manufacturing method described in the document US Pat. No. 3,026,568, the document US Pat. No. 4,279,579, the document WO 2009/153324 or the document WO 2012/168380. According to a particular embodiment, the shaping of the solid bitumen core can be carried out by dripping, in particular by means of a drum.

Other techniques can be used in the process for manufacturing the solid bitumen core, in particular molding, pelletizing, extrusion, etc. Preferably, the solid bitumen core particles have a longest average dimension ranging from 1 to 30 mm, preferably from 4 to 20 mm, more preferably from 4 to 15 mm.

Another object of the invention is a solid bitumen at room temperature in the form of granules obtainable by the implementation of the method according to the invention as described above. Such solid bitumen in the form of granules advantageously has the properties described above.

- Uses of solid bitumen granules:

Another object of the invention also relates to the use of solid bitumen granules at ambient temperature according to the invention as described above as road binder.

The road binder can be used to manufacture mixes, in combination with aggregates according to any known method.

Preferably, the solid bitumen at ambient temperature according to the invention is used for the manufacture of bituminous mixes.

Bituminous mixes are used as materials for the construction and maintenance of pavement bodies and their pavement, as well as for the realization of all road works. For example, superficial coatings, hot mixes, cold mixes, cold mixes, low emulsions, base layers, binding, hooking and rolling, and other combinations of a bituminous binder and road aggregate having particular properties, such as anti-rutting layers, draining asphalts, or asphalts (mixture between an asphalt binder and sand-like aggregates).

Another subject of the invention relates to a process for manufacturing asphalt mixes comprising at least one road binder and aggregates, the road binder being chosen from among the bitumens according to the invention, this process comprising at least the steps of:

heating the aggregates at a temperature ranging from 100 ° C to 180 ° C, preferably from 120 ° C to 160 ° C,

mixing the aggregates with the road binder in a tank such as a kneader or a kneading drum,

obtaining mixes. The method of the invention has the advantage of being able to be implemented without any prior step of heating the solid bitumen granules.

The method for manufacturing mixes according to the invention does not require a step of heating the granules of solid bitumen before mixing with the aggregates because in contact with the hot aggregates, the solid bitumen at ambient temperature melts.

The solid bitumen at ambient 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 road binder is carried out with stirring, then the stirring is maintained for at most 5 minutes, preferably at most 1 minute to allow to obtain a homogeneous mixture.

The solid bitumen in the form of granules according to the present invention is remarkable in that it allows the transport and / or the storage of road bitumen at ambient temperature under optimum conditions, in particular without there being agglomeration and / or adhesion solid bitumen during transport and / or storage, even when the ambient temperature is high. In addition, the coating layer of the granules breaks under the effect of contact with hot aggregates and shear and releases the bitumen base. Finally, the presence of the coating layer in the road binder mixture and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated bitumen base.

Another method of the invention also relates to a method for transporting and / or storing and / or handling road bitumen, said road bitumen being transported and / or handling of road bitumen. / or stored and / or handled in the form of solid bitumen granules at room temperature.

Preferably, the road bitumen is transported and / or stored at a high ambient temperature for a period greater than or equal to 2 months, preferably greater than or equal to 3 months.

Preferably, the high ambient temperature is from 20 ° C to 90 ° C, preferably from

20 ° C to 80 ° C, more preferably 40 ° C to 80 ° C, still more preferably 40 ° C to 60 ° C. The bitumen granules according to the invention have the advantage of maintaining their divided form, and therefore of being able to be handled, after storage and / or transport at a high ambient temperature. They have in particular the ability to flow under their own weight without flowing, which allows their storage in a packaging bags, drums or containers of all shapes and volumes and their transfer from this packaging to equipment, as a construction equipment (tank, mixer etc ...).

The bitumen granules are preferably transported and / or stored in bulk in 500 g to 100 kg or 500 kg to 1000 kg bags commonly known in the field of "Big Bag" road bitumens, said bags being preferably in hot melt material. They may also be transported and / or stored in bulk in cartons of 5 kg to 30 kg or in drums of 100 kg to 200 kg.

The various embodiments, variants, 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 :

1. Material and methods

The rheological and mechanical characteristics of the bitumens referred to in these examples are measured as shown in Table 1.

Table 1

The variation of the ball and ring softening temperature (TBA) is measured according to the standard NF EN 1427 of said composition between the sample extracted from the upper part of the sample tube and the sample extracted from the lower part of the tube. 'sample. 1.1 Composition of heart:

The bitumen base B ₂ is prepared from:

- a 35/50 grade bitumen base, denoted by Bi, having a penetrability P ₂₅ 34 1/10 mm and a TBA of 52.6 ° C and commercially available from TOTAL group under the trademark AZALT ^®;

- 1, 10 decanoic acid (sebacic acid) noted acid;

- the sulfur flower, noted crosslinking;

- zinc octanoate; noted scavenger.

The mass percentages used for the bitumen base are shown in Table 2 below.

Table 2

The bitumen is prepared in the following manner.

For the bitumen B ₂ , the bitumen base Bi is introduced into a reactor maintained at 160 ° C. with stirring at 300 rpm for two hours. The acid is then introduced into the reactor. The contents of the reactor are maintained at 160 ° C. with stirring at 300 rpm for 1 hour.

1.2 Coating composition

The coating compositions Ci and C ₂ are prepared from:

Oil: We used an oil RAE, that is to say an aromatic oil, marketed by TOTAL under the trademark Regenis 50 ®.

Organogelling compounds: Al additive of formula (I): 2 ', 3-bis [(3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl)] propionohydrazide (CAS 32687-78-8) marketed by the BASF company under the trademark Irganox MD 1024,

Additive A2 of formula (II A): N, N'-ethylene (stearamide) sold by Croda under the name Crodawax 140®.

The percentages by weight used for the preparation of the coating compositions C ₁ and C ₂ are shown in Table 3 below.

Table 3

The coating compositions Ci and C ₂ are prepared according to the following general method:

(i) The oil is heated, for example to 170 ° C;

(ii) The organogelling compound (s) is added, and is mixed, for example, for 1 hour at 170 ° C. with a stirring speed of 400 rpm;

(iii) When the organogelling additive (s) are completely dissolved, stirring and conditioning are maintained at a temperature at which the solution remains liquid until used for coating the granules.

2.1 General Method for Preparing Bitumen Cores of Granules According to the Invention

The bitumen base B ₂ is heated at 160 ° C. for two hours in the oven before being poured into a silicone mold having different holes of spherical shape so as to form the cores of solid bitumen. After observing the solidification of the bitumen in the mold, the surplus is leveled with a heated blade Bunsen burner. After 30 minutes, the solid bitumen in the form of uncoated granules is demolded and stored in a tray covered with silicone paper. The cores are then allowed to cool to room temperature for 10 to 15 minutes.

2.2 General Method for Preparing Bitumen Cores of 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 commercially available from Sandwik under the trade name of Rotoform.

Bitumen granules can also be obtained from the bituminous composition B ₂ poured into the tank of such a device and maintained at a temperature between 130 and 160 ° C.

A nozzle or a plurality of injection nozzles enable the transfer of the bitumen composition B ₂ into the interior of the double pastillating drum having a rotating outer drum, the two drums being provided with slots, nozzles and orifices for pastillation of bitumen drops through the first fixed drum and orifices having a diameter of between 2 and 8 mm from the rotating outer drum. The drops of bitumen are deposited on the upper face of a tread, horizontal, driven by rollers.

2.3 General method for coating the heart of granules

The granule cores Gi obtained above are dipped in one of the liquid coating compositions Ci or C ₂ , prepared previously, and then allowed to dry at room temperature.

This gives different coated granules:

the granules Gi ', obtained from the coating composition Ci, and

the granules G ₂ ', obtained from the coating composition C ₂ .

3. Evaluation of granule behavior: tacky appearance

The tacky appearance of the granules Gi 'and G ₂ ', prepared previously, is evaluated by a manipulator to the touch. For each type of granules, the manipulator takes a dozen granules and evaluates the stickiness of each of them by placing them first between two fingers and then trying to move the fingers of the surface of the granule.

The results obtained are given in the following Table 4.

Table 4

+: little sticky granules,

++: granules very little sticky. The two coating compositions Ci and C ₂ make it possible to obtain granules of bituminous bituminous material. The coating composition C ₂ , corresponding to the combination of the two organogelling compounds, makes it possible to obtain even less tacky granules.

Claims

1. Bitumen solid at room temperature in the form of granules comprising a core and a coating layer in which:

the core comprises at least one bitumen base,

and

the coating layer comprises at least:

An oil chosen from a hydrocarbon oil of petroleum or synthetic origin,

in which :

^■ Arl and Ar2 are independently from each other a benzene ring or a fused aromatic ring system of 6 to 20 carbon atoms, substituted by at least one hydroxyl group and optionally substituted by one or more alkyl groups C1 -C20, and

^■ R represents an optionally substituted divalent radical, whose main chain comprises 6 to 20 carbon atoms and at least one group selected from amide, ester, hydrazide, urea, carbamate, anhydride;

R ₂ - (NH) _n CONH- (X) _m - (NHCO) p (NH) _n -R ₂ '(II)

in which :

^■ the groups R ₂ and R ₂ 'are identical or different, represent a saturated or unsaturated hydrocarbon chain, linear, branched or cyclic, comprising 1 to 22 carbon atoms, optionally substituted and optionally comprising one or more heteroatoms such as N , O, S, C ₅ -C ₂ 4 hydrocarbon rings and / or hydrocarbon heterocycles C4-C24 comprising one or more heteroatoms such as N, O, S, and R ₂ 'may be H;

The group X represents a hydrocarbon chain, saturated or unsaturated, linear, cyclic or branched, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more heteroatoms such as N, O, S, hydrocarbon-based rings; C5-C24 and / or C4-C24 hydrocarbon heterocycles comprising one or more heteroatoms such as N, O, S;

■ n, m and p are integers having a value of 0 or 1 independently of each other;

R ₅ - (COOH) _z (V)

in which :

R ₅ 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.

2. Bitumen according to claim 1, wherein the hydrocarbon oil is selected from hydrocarbon oils of petroleum origin.

3. Bitumen according to any one of the preceding claims wherein the hydrocarbon oil is selected from aromatic oils having an aromatic content of between 30 and 95% by weight, preferably between 50 and 95% by weight, more preferably between 60 and 95% by weight relative to the total mass of the aromatic oil.

4. Bitumen according to any one of claims 1 and 2 wherein the hydrocarbon oil is selected from paraffmic oils having a total content of paraffmic compounds of at least 50% by weight relative to the total mass of the paraffmic oil.

Bitumen according to claim 4, wherein the paraffmic oil has the respective contents:

(i) a total content of paraffinic compounds of between 50% and 90%;

(ii) a total content of naphthenic compounds of between 5% and 25%; and (iii) a total content of aromatic compounds of between 5% and 25%, the percentages being expressed by weight relative to the total mass of the paraffinic oil.

A bitumen according to any one of the preceding claims, wherein the coating layer comprises from 80% to 99.9% of at least one oil, by weight based on the total weight of the coating layer.

Bitumen according to any one of the preceding claims, in which the coating layer comprises from 0.1 to 10%, preferably from 0.2% to 5% by weight, more preferably from 0.5% to 3.5%. % by weight of organogelling compound relative to the total mass of the coating layer.

8. Bitumen according to any one of the preceding claims, wherein the core further comprises at least one compound selected from organogelling compounds.

Bitumen according to any one of the preceding claims, wherein the core further comprises 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, with the understanding that penetrability is measured according to EN 1426 and that the TBA is measured according to EN 1427.

A method of manufacturing a bitumen according to any of claims 1 to 9, which process comprises:

i) shaping the core from at least one bitumen base,

ii) coating the core on all or part of its surface with a coating composition, iii) optionally, drying the granules obtained in step ii) at a temperature ranging from 20 to 60 ° C, for a period ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours.

11. A bituminous mix comprising a bitumen according to any one of claims 1 to 9 and which further comprises aggregates and optionally mineral and / or synthetic fillers.

12. asphalt mixture according to claim 11 which is a road asphalt, bituminous concrete, or bituminous mastic.

13. A process for manufacturing asphalt comprising at least one road binder and aggregates, the road binder being chosen from bitumens according to any one of claims 1 to 9, this process comprising at least the steps of:

heating the aggregates at a temperature ranging from 100 ° C. to 180 ° C., preferably from 120 ° C. to 160 ° C.,

- Obtaining mixes.

14. The method of claim 13, which comprises no step of heating the road binder before mixing with the aggregates.

15. A method for transporting and / or storing bitumen, said bitumen being transported and / or stored in the form of solid bitumen at ambient temperature according to any one of claims 1 to 9.