OA19100A - Solid bitumen at room temperature. - Google Patents

Abstract

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: • 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). Process for the production of bitumen granules and their use as a road binder, in particular for the manufacture of asphalt. Process for the manufacture of asphalt mixes from bitumen granules as well as a method of transport and / or storage and / or handling of bitumen granules.

Description

SOLID BITUMEN AT ROOM TEMPERATURE

Technical area

The present invention relates to a bitumen composition in divided form, which is solid at room temperature. The present invention also relates to a process for preparing a solid bitumen composition at room temperature as well as its use as a road binder, in particular for the production of mixes.

The present invention also relates to a process for the production of mixes from solid bitumen according to the invention as well as to a process for transporting and / or storing and / or handling a solid bitumen composition at room temperature according to the invention. 1 invention.

State of the prior art

Π 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 usually in the form of a black material that is highly viscous, even solid at room temperature, which becomes fluid on heating.

Typically, bitumen is stored and transported hot, in bulk, in tankers or by ships at high temperatures in the range of 120 ° C to 160 ° C. However, the storage and transport of hot bitumen have certain drawbacks. On the one hand, the transport of hot bitumen in liquid form is considered dangerous and it is very tightly controlled from a regulatory point of view. This mode of transport does not present any particular difficulties when the equipment j and the transport infrastructure are in good condition. Otherwise, it can become problematic: if the tanker is not sufficiently insulated, the viscosity of the bitumen J may increase during a too long journey. The bitumen delivery distances are therefore limited. On the other hand, keeping bitumen at high temperatures in tanks or tankers consumes energy. In addition, maintaining bitumen at high temperatures for a long period of time can affect the properties of the bitumen and thus change the final performance of the asphalt.

To overcome the problems of transporting and storing hot bitumen, packaging allowing the transport and storage of bitumens at room temperature have been developed. This mode of transporting bitumen in packaging at room temperature represents only a small fraction of the quantities transported

DUPLICATE ^J 19100

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- J in the world, but it corresponds to very real needs for geographic areas that are difficult and expensive to access by traditional means of transport.

-J As an example of packaging allowing cold transport currently used, we can cite the packaging of bitumen at room temperature in * 5 metal drums. This method is increasingly questionable from an environmental point of view because the bitumen stored in the drums must be heated before it is used as a road binder. However, this operation is difficult to implement for

Π this type of packaging and the drums constitute waste after use. On the other hand, the storage of bitumen at room temperature in drums leads to FJ 10 losses because the bitumen is very viscous and part of the product remains on the walls of the drum during

----------------- Fràtisvâsèiûèiit in the tanks of the asphalt production units. As for the handling and transportation of bituminous products in these drums, they can be difficult and dangerous if specialized drum handling equipment is not available from carriers or where the bitumen is used.

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

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

Application WO 2016/016318 describes bitumen granules comprising a chemical additive which can be a mono-buûrfpolyacidê, a fiydrazide, or a diàmid. These bitumen granules allow the transport and / or the storage and / or the handling of the bitumen at ambient temperature without the latter creeping, as well as the reduction of their adhesion and agglomeration between them.

Application US 2011/0233105 describes asphalt that is solid at room temperature in the form of granules comprising a core and a coating layer. The core is made from recycled materials and an asphalt-based binder. Coating layer

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LJ can include one or more water resistant polymers, wax or fines, q This coating layer is intended to prevent the adhesion of particles to each other, but also to adjacent surfaces during storage. This document does not disclose ~ i the content of viscosifying compound relative to the total mass of the layer of ^L 5 coating. It also does not disclose the viscosity of the compounds entering into the composition of the coating layer.

^L FR 2 992 654 discloses bituminous compositions comprising a bitumen, a

Π first additive comprising at least one fatty acid ester function and a second additive comprising at least one organogelling compound. These compositions present

Π __________ 10 improved thermal susceptibility and can be used for applications

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. road and industrial. ^:::

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

There is therefore a need to provide a bitumen composition that can be transported and / or stored and / or handled at room temperature, making it possible to overcome the drawbacks of the prior art.

An objective of the present invention is to provide a bitumen composition which can be transported and / or stored and / or handled at high ambient temperature, and the properties of which are retained over time.

In particular, the aim of the present invention is to provide a bitumen composition which can be transported and / or stored for a period greater than 2 months, preferably 3 months, and at elevated ambient temperature, in particular at a temperature below 100 °. C, preferably 20 ° C to 80 ° C.

Another objective of the invention is to provide a bitumen composition that is easy to handle, in particular at high ambient temperature, in particular at a temperature ranging up to 100 ° C, preferably from 20 ° C to 80 ° C.

In particular, the aim of the present invention is to provide a bitumen composition which can be easily handled after a period of transport and / or prolonged storage at high ambient temperature, in particular during a period of transport.

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J and / or storage greater than 2 months, preferably greater than 3 months, and at a temperature q of up to 100 ° C, preferably between 20 ° C and 80 ° C.

An objective of the present invention is to provide a γί bitumen composition in a form which allows it to flow in solid form at ambient temperature, so that it can be handled without loss of material. We sought to

Π provide a bitumen composition which is in a form suitable ^L 'packaged in a packaging, unpacking, the transfer to a or equipment, even at a high ambient temperature without the need for the ^LJ heat, and without loss of material. The proposed bitumen is in divided and solid form at

Π 10 room temperature so that it satisfactorily solves the problems mentioned above.

Another objective is to provide an industrial and economical process for manufacturing a bitumen composition that can be transported and / or stored and / or can be handled at room temperature,

Another objective of the invention is to provide an industrial and economical process for manufacturing asphalt mixes from a bitumen composition that can be transported and / or stored and / or handled at room temperature.

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

Summary of the invention

The invention relates to a bitumen which is solid at room temperature in the form of

[J granules comprising a core and a coating layer in which:

core island includes at least one bitumen base, r and

- the coating layer comprises at least:

An oil chosen from a hydrocarbon-based oil of petroleum or synthetic origin, = 1 "at least one organogelating compound chosen from the compounds of general formula (I), (II) or (V):

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^Ί 19100 l ⁵ η Arl-R | -Ar2 (I) in which: Π Arl and Ar2 represent, independently of each other, a benzene ring or a condensed 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, including Π 10 la. nrincinal chain has 6 to 20 carbon atoms and ΙΊ P Γ P at least -one group chosen from amide and ester functions, _n R ₂ - (NH) _n CONH- (X) _m - (NHCO) _p (NH) _n -R ₂ '(II). J in which: _n 15 the groups R ₂ and R ₂ ′, identical or different, represent LJ a saturated or unsaturated, linear, r, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, LJ optionally substituted, and optionally comprising one or more heteroatoms such as N, 0, S, LJ 20 hydrocarbon-based C5-C24 rings and / or p C ₄ -C ₂₄ hydrocarbon heterocycles comprising one or more heteroatoms such as N, UO, S, and R ₂ 'can be H; ri “the group X represents a hydrocarbon chain, saturated 'J or unsaturated, linear, cyclic or branched, comprising from 1 to η 25 22 carbon atoms, optionally substituted, and ^u optionally comprising one or more heteroatoms such ) As N, 0, S, hydrocarbon rings C5-C ₂₄ and / or ^u hydro carbonaceous monocyclic C ₄ -C ₂₄ comprising a 11 or more heteroatoms such as N, O, S; '30 “n, m and p are integers having a value of 0 or 1 i independently of each other;

IR ₅ - (COOH) _z (V) lJ

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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 varying from 2 to 4.

in which :

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

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

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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 mass relative to the total mass of the paraffinic oil.

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- * Advantageously, according to this variant, the paraffinic oil has the respective j contents:

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

LJ (ii) a total content of naphthenic compounds of between 5% and 25%; and j-, 20 (iii) a total content of aromatic compounds of between 5% and 25%, the

U percentages being expressed by mass relative to the total mass of the paraffinic oil.

According to a preferred embodiment, the coating layer comprises 80%

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[99.9% of at least one oil, by mass based on the total mass of the layer of a

coating.

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According to a preferred embodiment, the coating layer comprises from 0.1 to

[_. 10%, preferably from 0.2% to 5% by mass, more preferably from 0.5% to

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The 3.5% by mass of organogelating compound based on the total mass of the coating layer.

n According to a preferred embodiment, the heart further comprises at least one compound selected from 5 ^J 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 temperature of Γ] ball and ring softening (TBA) ranging from 115 ° C at 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 LJ, ^1Q standard EN 1427.

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

i) shaping the core from at least one bitumen base, ii) coating the core over all or part of its surface with a coating composition, iii) optionally, drying the granules obtained by 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.

A further subject of the invention is a bituminous coating which comprises a bitumen as described above and in detail below and which further comprises aggregates and optionally mineral and / or synthetic fillers.

} 25 According to a preferred embodiment, the bituminous mix is a road mix, a bituminous concrete, or a bituminous mastic.

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

DUPLICATE ^; 19100 η “ ¹ - heating the aggregates to 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 mixer n or a mixer drum,

- obtaining of asphalt.

According to a preferred embodiment, the method does not include a step of

Ej heating the road binder before mixing it with the aggregates.

JJ 10 The invention also relates to a method for transporting and / or storing bitumen.

said bitumen being transported and / or stored in the form of solid bitumen at temperature

Γ] ambient as described below and in detail below.

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detailed description

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

The term “ambient temperature” is understood to mean the temperature resulting from the climatic conditions in which the road bitumen is transported and / or stored and / or handled. More precisely, the ambient temperature is equivalent to the temperature reached during the transport and / or the storage and / or the handling of the road bitumen, it being understood that the ambient temperature implies that no heat input is brought 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.

The term “bitumen which is solid at room temperature” is understood to mean a bitumen exhibiting a solid appearance at room temperature regardless of the conditions of transport and / or storage and / or handling. More precisely, by solid bitumen at room temperature is meant a bitumen which retains its solid appearance throughout transport and / or storage and / or handling at room temperature, that is to say DUPLICATA

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I 9 * say a bitumen which does not creep at room temperature under its own weight and moreover, which does not creep when subjected to pressure forces resulting from the conditions of transport and / or storage and / or handling.

n By "coating layer covering any portion of the surface of the heart" is ^J 5 means that the coating layer covers at least 90% of the surface of the heart,

Π preferably at least 95% of the surface of the heart, more preferably at least 99% of the surface of the heart.

pj By "penetrability" is meant here the measurement known as "needle penetrability" which is carried out by means of a standardized test NF EN 1426 at 25 ° C (P25). This

Π 10 penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). Penetrability at Γ needle, measured at 25 ' ^J C, according to the standardized test NF EN lI

------- 1136, represents the measurement of the penetration in a bitumen sample ^ after a time of 5 seconds, of a needle whose weight with its support is 100g. The standard NF EN 1426 replaces the approved standard NF T 66-004 of December 15, 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated November 20, 1999).

The term “softening point” is understood to mean the measurement known as “ring ball softening point” 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 d. The steel of standard diameter, after having passed through the material to be tested (glued in a ring), reaches the bottom of a standardized vessel filled with a liquid which is gradually heated, and in which the apparatus has been immersed.

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

The expression "between X and Y" includes limits, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, 30 Y and all values ranging from X to Y.

A first object of the invention relates to a bitumen which is solid 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:

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- the core comprises at least one bitumen base and,

- the coating layer comprises at least:

• an oil chosen from a hydrocarbon oil of petroleum origin i ·

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- 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 bringing into contact:

= LÛ -------- = - one or more bitumen bases, and ------------------------------- ------------

- optionally at least one organogelator compound,

-----------— évcnlucllcmuil a biai, ---------------------------------- ----------------

- optionally at least one anti-caking compound.

For the purposes of the invention, the terms "bitumen" and "road bitumen" are used equivalently and independently of each other. By "bitumen" or "road bitumen" is meant any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more additives. When said compositions are intended for road application, they are more frequently referred to under the name of “road bitumen”. The invention also finds applications in fields other than the road field.

Among the bitumen bases that can be used according to the invention, there may be mentioned first of all bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or tar sands and bitumens from the refining of crude oil. . The bitumen bases according to the invention are advantageously chosen from bitumen bases obtained from the refining of crude oil. The bitumen bases can ------- be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches. The bitumen bases can be obtained by conventional methods of manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumen bases can optionally be vis-reduced and / or deasphalted and / or air-rectified. It is common practice to perform vacuum distillation of atmospheric residues from atmospheric distillation of crude oil. This manufacturing process corresponds,

DUPLICATE ^L J consequently, to the succession of an atmospheric distillation and a q vacuum distillation, the charge feeding the vacuum distillation corresponding to the

J atmospheric residues. These vacuum residues from the vacuum distillation tower

T can also be used as bitumens. It is also common to inject air into a charge usually made up of distillates and heavy products.

Π from the vacuum distillation of atmospheric residues from the distillation of petroleum. This process makes it possible to obtain a blown base, or semi-blown or oxidized or air-rectified or partially air-rectified.

'' The different bitumen bases obtained by refining processes can be

Π 10 combined to obtain the best technical compromise. The bitumen base can also be a recycling bitumen base. Bitumen bases can be ü ΰ i I bases

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

According to the invention, the blown bitumens can be manufactured in a blowing unit, by passing a flow 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, 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 penetrability measured at 25 ° C according to standard EN 1426 from 5 to 330 1/10 mm, preferably from 20 to 220 1 / 10 mm.

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As is well known, the so-called “needle penetrability” measurement is ηΐ carried out by means of a standardized test NF EN 1426 at 25 ° C (P25) · This penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm). The η needle penetrability, measured at 25 ° C, according to the standardized test NF EN 1426,

J 5 represents the measurement of the penetration into a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100 g. ^J standard NF EN 1426 replaces approved standard NF T 66-004 of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated ^J November 20, 1999).

3__________10________ According to one embodiment of the invention, the bitumen base can also

1. ................................................ ....... ............................ ............... .......................... ........................ .........

include at least one known bitumen elastomer such as co-polymers

-------- (styrene and butiidièiic block copolymer), SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene-styrene), SBS * (styrene-butadiene block copolymer) styrene star), SBR (styrene-b-butadiene-rubber), EPDM 15 (modified ethylene propylene diene). These elastomers can also be crosslinked according to any known process, for example with sulfur. Mention may also be made of elastomers produced from styrene monomers and from butadiene monomers allowing 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 mass, preferably from 1% to 15% by mass, more preferably from 2% at 12% by mass 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 oleiinic 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 mass, preferably from 0.1% to 10% by mass, more preferably from 0.5 % to 6% by mass 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.

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Advantageously, according to this embodiment, the bituminous i composition forming the heart of the granules comprises from 2 to 30% by pitch mass relative to the ^J total weight of the composition, preferably from 3 to 20% by weight of pitch by ratio ί to the total mass of the bituminous composition forming the core of the granules.

^{May 3} According to an embodiment of the invention, the bituminous composition which comprises the heart of the granules comprises at least one anti-caking agent.

Advantageously, according to this embodiment, the composition forming the core Ί of the bitumen granules comprises between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass. mass of at least one] 10 anti-caking agent relative to the total mass of the bituminous composition forming the core of said granules.

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

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

- Olefinic polymer additive

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

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

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

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Monomer A is chosen from vinyl acetate and C 1 to C 4 alkyl acrylates or methacrylates.

³ Monomer B is chosen from glycidyl acrylate and η 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, from 'J preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being

- formed from units derived from ethylene.

H 10 (c) The copolymers result from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, onto a polymer substrate. The substrate - oonoiota polymer in one. polymer selected from polyethylenes, especially low density polyethylenes, polypropylenes, random or block copolymers, preferably random, of ethylene and vinyl acetate and random or block copolymers, preferably random, of ethylene and of C 1 to C ₆ alkyl acrylate or methacrylate, comprising from 40% to 99.7% by mass, preferably from 50% to 99% by mass of ethylene. Said graft copolymers comprise from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of grafted units obtained from monomer B.

Advantageously, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene (b), of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen from acrylate. glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0, 5% to 15% by mass, preferably from 2.5% to 15% by mass of units derived from monomer B, the remainder being formed from units derived from ethylene.

- The pitch:

The bitumen base is chemically different from the pitch used. Therefore, the bitumen base and the pitch cannot be used as a replacement for the other because their

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J chemical characteristics are different. Pitch can be used in

Ί mixture in the bitumen base.

^J According to one embodiment of the invention, the pitch is a blown pitch. Within the meaning of

Ί the invention, be used independently of each other, the terms "pitch blown" and ^J 5 "oxidized pitch".

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

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

In the description, the terms "pitch", "petroleum pitch" and "deasphalting pitch" will be used independently of each other.

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

You can get the "petroleum pitch" by two methods: the ^era process:

The vacuum distillation residue is dealphated by addition of a suitable solvent, such as propane, thereby precipitating the pitch and separating it from light fractions such as deaphalted oil.

_____________2 ^nd process: ______________: ______________________________________________________________ The vacuum distillation residue is subjected to extraction with solvent, and more precisely with furfuraldehyde. This heterocyclic aldehyde has the particularity of selectively solubilizing aromatic and polycyclic compounds. This process thus makes it possible to eliminate the aromatic extracts and to recover the “petroleum pitch”.

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

Preferably, the oxidized pitch used according to the invention is obtained by oxidation of a mixture comprising pitch and a diluent, such as a light gasoline, also

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- Called "flux" subjected to an oxidation operation in a blowing tower in the presence of a catalyst, at a set temperature and at a given pressure.

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

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

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

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

The addition of a pitch with the mechanical characteristics presented above in a bituminous composition forming the core of the granules of the invention makes it possible to improve the modulus properties of said bituminous composition and also to improve the modulus properties of the granules. bituminous mixes. In addition, the addition of the pitch according to the invention in a bituminous composition constituting 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 relative to a bituminous composition L without pitch.

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Ί 17 ^L The bituminous composition making up the core of the granules of η the invention can be prepared by a process comprising at least the steps of:

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

Π · Introduction of the pitch into the bitumen base, · Stirring of the mixture at a temperature ranging from 140 to 180 ° C up to

U 1 'obtaining a homogeneous mixture.

‘It has been observed 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 its introduction into the heated bitumen base. Such a mode of

This 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

IJ ----------------- bitumen base. Although the pitch has usually increased a melting temperature above 220 ° C., it dissolves in bitumens at the usual temperatures for preparing bituminous compositions. The process for manufacturing the bituminous composition constituting the core of the granules of the invention is easy to

H implement and does not require hot transport over long distances 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 and divided form, preferably in the form of granules. This shape facilitates the handling of the pitch for its use in the manufacture of the bituminous composition constituting the heart of the Q granules of the invention.

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

[J Pitch granules can have, within the same population of granules, one or more shapes chosen from a cylindrical, spherical or ovoid shape.

y 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, plus

I I preferably from 2 to 30 mm. For example, the use of a channel allows

DUPLICATE ο

ϋ

ί]

D

[.] control the production of granules of a chosen size. A sieving makes it possible to select granules according to their size.

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

1Ώ

- Anti-caking agent: '

----------- Lo oompoaé anti-caking agent can be used as an additive in the composition — which is the core of the granules.

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

It can 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; fines, also called fillers, generally with a diameter of less than 125 µm, such as siliceous fines, with the exception of limestone fines; ultrafine; sand such as fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular of pine; rice hull ash; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as ________alumina hydrates; silica; silica derivatives such as silicates, silicon hydroxides and other sificon oxides; silica fumes; plastic powder; lime; the plaster ; rubber crumb; powder of polymers, such as styrene-butadiene (SB) copolymers, styrene-butadiene-styrene (SBS) copolymers and mixtures of these materials.

Advantageously, the anti-caking compound is chosen from: fines, generally with a diameter of less than 125 μm; silica fumes; the residues of

DUPLICATA ¹ 19100 ¹⁹ 'woods such as lignin, conifer needle powders and conifer cone powders; their mixtures.

^LJ By way of example, the anti-caking agent can be chosen from silica fumes, n Preferably, the anti-caking compound is chosen from silica fumes.

^J 5 In particular, when the composition of which the core of the granules is made

Π comprises at least one anti-caking compound, it is preferably chosen from ice silica fumes.

When the granules according to the invention are coated, over all or part of their surface, with a coating layer comprising an anti-caking compound, said fl 10 anti-caking compound is preferably chosen from silica fumes.

According to one embodiment, the core of the granules consists of a ⁷

Îj f

J

------- composition comprising at least one anti-caking agent, preferably chosen from silica fumes, and the surface of said granules is covered, at least in part, with a coating layer comprising an anti- compound. agglomerating agent, preferably chosen from silica fumes.

For the purposes of the invention, the compounds "silica fume" and "fumed silica" have the same chemical definition and are registered under the same CAS number 112 945-52-5. Therefore, within the meaning of the invention, these compounds can be used interchangeably. By “fumed silica” is meant either a fumed silica or a derivative of pyrogenic silica.

By "fumed silica" is meant a compound obtained by the vapor phase hydrolysis of chlorosilanes, such as silicon tetrachloride, in a flame of oxygen and hydrogen. Such processes are generally designated as pyrogenic processes whose overall reaction is: S1Cl4 + H2 + O2 - * S1O2 + 4 HCl.

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

Preferably, the fumed silica compound is fumed silica.

According to one embodiment of the invention, the fumed silica compound

Q has a specific surface area of between 25 and 420 m / g, preferably between 90 and 330 m / g, more preferably between 120 and 280 m / g.

DUPLICATE '19100

Π ²⁰ t- 'The specific surface of the fumed silica defined in m ² / g commonly called “surface area” or “SA” is measured according to the method of S. Brunauer, ^{1 2} PH Emmet and L Teller, J. Am. Chemical Society, 60: 309 (1938) (BET).

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

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

Q 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

Π 10 total weight of the fumed silica compound.

According to one embodiment of the invention, the fumed silica compound is

------- chosen from a hydrophilic fumed silica compound, a hydrophobic fumed silica compound and mixtures thereof.

Preferably, the fumed silica compound is a hydrophilic fumed silica compound.

By "hydrophilic" is meant a compound which is miscible with water in all proportions.

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

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

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

- hydrophilic pyrogenic silicas, as described in WO 2009/071467, WO

2011/000133 filed in the name of Degussa AG or Degussa Gmbh,

- silica fumes made hydrophobic by treatment with polysiloxanes as described in WO 20 08/141932, 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.

DUPLICATE

Γ 3 Γ 21: 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 in the form of a mixture with within i of a coating composition. ^J 5 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 under the ^! in the form of a powder or in dispersion in a solvent which evaporates after application. 1 Preferably, when the coating composition comprises at least one fumed 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 1 ujinpusitiuii of your garment, plus small amount of 20 to 40% in weight. 1 Reference. the solvent is an organic solvent or water. By solvent Γ organic means any solvent immiscible with a bitumen, such as an alcohol, by | example ethanol. The silica films used in the invention are commercially available ] and for example can be sold by Evonik Degussa under the brand AEROS IL®, such as, for example, AEROSIL®200, by Cabot Corporation under the trademarks CABO-SIL® and CAB-O-SPERSE® or by Wacker Chemie AG under the brand HDK®. ] 20 - The composition forming the heart of the granules: j The composition forming the core of the granules comprises: - one or more bitumen bases, and - optionally at least one organogelator compound, 25 - possibly a pitch. Optionally, it can also include: ι. f L Γ L γ ί L one or more additive additives chosen patnii Léà elastomers, olefinic polymer adjuvants, anti-caking compounds. Advantageously, the composition forming the core of the granules, comprising a 30 bitumen base supplemented with at least one organogelating compound and / or at least one pitch, has a target penetrability ranging from 5 to 45 1/1 Omm and / or a temperature | target ball and ring softening (TBA) greater than or equal to 90 ° C, being DUPLICATE

^{22 2} understood that the penetrability is measured at 25 ° C according to standard EN 1426 and TBA n according to standard EN 1427.

'These characteristics are achieved by methods known to those of

O business, by hot mixing the component (s) in the bitumen base ¹ 5 in the appropriate amounts as indicated above for each category of

ΓΊ 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 ^L without degrading the properties of the composition forming the heart of the granules.

The composition thus obtained is directly used in the process of

Π r

U

ΓΙ

LJ η

ü

-------- manufacture of bitumen granules with a core / shell 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 mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one organogelator compound, relative to the total mass of bitumen of said granules.

Advantageously, the bituminous composition forming the core of the granules 20 comprises:

- one or more bitumen bases,

- between 0.1% and 5% by mass, preferably between 0.5% and 4% by mass, more preferably between 0.5% and 2.5% by mass of at least one organogelator compound relative to the total mass of bitumen of said granules, and

- between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4% and 15% by mass of at least one anti-caking 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 of the aromatic or paraffinic type.

According to one embodiment, the oil is composed of 90 to 100% by mass of at least one hydrocarbon oil of petroleum origin, preferably 95 to 100%,

Even better DUPLICATES from 98 to 100% by mass of at least one hydrocarbon oil of petroleum origin. Even more preferably, the oil consists of a hydrocarbon oil of petroleum origin or of 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 an aromatic compound content of between 30 and 95% by mass, advantageously between 50 and 95% by mass, more advantageously between 60 and 95% by mass relative to the total mass of aromatic oil (SARA method:

Saturated / Aromatics / Resins / Asphaltenes).

More preferably, the aromatic oils have a saturated compound content of between 1 and 20% by mass, advantageously between 3 and 15% by mass, more advantageously between 5 and 10% by mass (S ARA method: 15 Saturates / Aromatics / Resins / Asphaltenes).

More preferably, the aromatic oils have a content of resin compounds of between 1 and 10% by mass, advantageously between 3 and 5% by mass, (SARA method: Saturates / Aromatics / Resins / Asphaltenes).

n The contents of saturated, resin and aromatic compounds mentioned in this application are determined according to the ASTM D2140 standard, in% by mass relative to the mass of the oil.

p More preferably, the aromatic oils have a kinematic viscosity at

U 100 ^c C between 0.1 and 150 mm ^? 7s, advantageously between 5 and 120 mm / s, more advantageously between 7 and 90 mm / s (ASTM D 445 method).

L

More preferably, aromatic oils have a Cleveland il O CO flash point

Î greater than or equal to 150 ° C., advantageously between 150 ° C and 600 ° C, more advantageously between 200 ° C and 400 ° C (Method EN ISO 2592).

L

DUPLICATE IT! ) • J

More preferably, the aromatic oils have an aniline point of between 20 C and 120 C, advantageously between 40 C and 120 C (ASTM D611 method).

More preferably, the aromatic oils have a density at 15 C

3 3 between 400 kg / m and 1500 kg / m, advantageously between 600 kg / m

3 3 and 1200 kg / m, more preferably between 800 kg / m and 1000 kg / m (Method ASTM D4052).

According to this advantageous embodiment, the aromatic oil comprises ------- aïomallques extracts of peLwle residues, obtained by extraction or dearomatization of residues from the distillation of petroleum cuts.

Aromatic extracts are by-products of the refining process of crude oils, obtained in particular from the products of the vacuum distillation of atmospheric residues. They result from a single or double extraction of raffinai which can be used in lubricants, using a polar solvent.

The different extracts are classified into different categories according to their process of obtaining and are as follows:

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

- MES (Mild Extract Solvate in English or mild extraction solvent),

- TDAE (Treated Distillate Aromatic Extract in English or treated aromatic distilled extract),

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

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

For example, the aromatic oils which can be used according to the invention can be chosen from the following products sold by the company TOTAL under the names: Plaxolène 50® (also sold under the trade name Régénis 50®), Plaxolène TD346® and Plaxolène MS 132® .

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

DUPLICATE

Oils corresponding to the characteristics below and which can be used according to the invention are obtained by the deasphalting processes for vacuum residues (RSV) obtained from petroleum refining, for example by deasphalting using a C3 solvent. C6, preferably 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, the residues resulting from the vacuum distillation (RSV) are separated according to their molecular mass in the presence of solvent Γ3 to C6 (by PYPtnplp prnpan ^) T ' hpilft r1i'lp ΠΑΩ ΗΊΊΊΐί obtained is rich in paraffin, has a very low asphaltene content, has an evaporation temperature between 440 ° C and 75O ° C, and an API gravity much higher than that of vacuum residues.

The API gravity or API gravity of an oil (in English "API gravity" for "American Petroleum Institute gravity") can be obtained from the following formula (1):

^{Gapi =} ^ ¹³¹ ' ⁵ a

with:

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

- d, the density at 16 ° C (60 ° F) of the oil considered (expressed without units) 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 from which the PAO oil originates and on the refining process used. Those skilled in the art know how to determine the respective contents of paraffinic, naphthenic and aromatic compounds in a DAO oil, for example using the SARA fractionation method also described in Lee et al 2014, Fuel Processing Technology 119: 204-210 and thereby selecting the appropriate DAO oil for the preparation of the gelled oil composition according to the invention.

DUPLICATE

The contents of paraffinic, naphthenic and aromatic compounds mentioned in the present application are determined according to the standard

ASTM D2140,% by mass based on 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 mass of at least one aromatic oil, preferably a RAE oil, and from 0 to 10% by mass of one or more other oils.

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

Preferably, the oil is a paraffinic oil, more preferably a DAO paraffinic oil.

The other oils used can be chosen from oils of petroleum origin, oils of vegetable origin and mixtures thereof.

For example, oils of vegetable origin can be chosen from rapeseed, sunflower, soybean, linseed, olive, palm, castor, wood, corn, squash, grape seed oils. , 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 bitumen which is solid at room temperature in the form -------------- of granules according to the invention comprises at least one organogelating compound .

The core of the bitumen which is solid at room temperature in the form of granules according to the invention can also comprise at least one organogelating compound.

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

DUPLICATEj i

i!

Preferably, the composition forming the core of the bitumen granules which are solid at room temperature comprises at least one organogelating compound in an amount suitable for this composition to be solid at room temperature and in divided form.

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

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

----- Arl-Ri-Ar2 (1), ------------------------------------ --------------------- where i -------------------------- ------------------------------------------- • Arl and Ar2 independently represent l 'on the other hand a benzene ring or a system of condensed aromatic rings 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 • Ri represents a 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.

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

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

As an example of a compound of formula (I), there may be mentioned 2 ’, 3-bis [(3- [3, 5-diim-butyl-4-hydroxyphen.yl] propionyl)] propionohydrazide.

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

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

DUPLICATE

Ο

[J

U

l]

- the groups R ₂ and R ₂ ', which are identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted by one or more hydroxyl groups or amine groups, 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 and R2 ′ 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 NOS of C5-C24 hydrocarbon rings and / or C4-C ₂₄ hydrocarbon heterocycles -------- comprising one or more heteroatomgs such as N _t O _t S; -------------------- --------

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

According to this variant, when the integer m has a value of 0 and when the integer pa has a value of 1, then the groups R ₂ - (NH) _n C0NH and NHCO (NH) _n -R ₂ 'are covalently linked and together form a CONH-NHCO hydrazide bond. The R ₂ group, or the R ₂ 'group, 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, a condensed aliphatic, partially aromatic polycyclic system or fully aromatic, each ring comprising 5 or 6 atoms.

Still according to this variant, when the integer m has a value of 1, then the group R ₂ , the group R ₂ 'and / or the group X 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, partially aromatic or fully aromatic condensed polycyclic system, 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 C4H9, CjHu, C9H19, C11H23, C12H25, C17H35, C18H37, C21H43, C22H45.

According to a first preferred embodiment, the group X represents a linear, saturated hydrocarbon chain comprising from 1 to 22 carbon atoms,

DUPLICATE advantageously from 1 to 12 carbon atoms, more preferably from 1 to 10 n carbon atoms. Preferably, the X group is chosen from C2H4 groups,

C ₃ H ₆ .

ΓΊ According to a second preferred embodiment, the X group can also be a cyclohexyl group or a phenyl group, the radicals R ₂ - (NH) nCONH- and A NHCO (NH) _n -R ₂ 'can then be in the ortho position , meta or para. Furthermore, the radicals R ₂ - (NH) _n CONH- and -NHCO (NH) _n -R ₂ 'can be in the cis or trans position.

Q relative to each other. In addition, when the radical X is cyclic, this ring can be substituted by groups other than the two main groups R ₂ Π 10 (NH) nCONH- and -NHCOiNHVR? '.

According to a third pre-tested embodiment, the group A represents

D ---------------- two cycles of 6 carbons, optionally substituted, linked by a CH _{2j group}

U these rings being aliphatic or aromatic. In this case, the group X is for example:

Advantageously, according to this variant, the organogelator compound is a compound of general formula (II) chosen from hydrazide derivatives such as compounds C5H11-CQNH-NHCO-C5H11, C9H19-CONH-NHCO-C9H19, C11H23-CONHNHCO-C11H23, C17H35-CONH-NHCO-C17H35, or C ₂ 1H43-CONH-NHCO-C ₂ 1H43; diamides such as N, N'-ethylenedi (laurylamide) of formula CnH ₂ 3-CONH-CH ₂ CH2-NHCO-C11H31, N, N'-ethylenedi (myristylamide) of formula C13H ₂₇ -CONHCH ₂ -CH ₂ -NHCO-Ci3H27, N, N'-ethylenedi (palmitamide) of formula Ci 5H31-CONH25 CH ₂ -CH ₂ -NHCO-Cî5H3i, N, N'-ethylenedi (stearamide) of formula Cr / Hss-CONIlCH2-CH2 -NHCO-C17H35; and ureid derivatives such as 4,4'bis (dodecylaminocarbonylamino) diphenyhnethane of formula C12H25-NHCONHC ₆ H ₄ -CH ₂ -C ₆ H4-NHCONH-C12H ₂ 5.

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

U Preferably, the compound of general formula (II) is chosen from those which rj satisfy the condition: the sum of the numbers of the carbon atoms of R ₂ , X and R ₂ '

LJ

DUPLICATE

U

Π

Π

D

Π

Π l

LJ

L 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 5 R2 'is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14.

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

R ₂ -CONH- (X) _ltI -NHCO-R ₂ '(IIA) in which R ₂ , R ₂ ', m and X have the same definition as above.

Preferably, in formula (IIA) when m = 1, the group X represents

------- tinfi fihaînc linear saturated hydrocarhnnén compressing from 1 to 22 carbon atoms, advantageously X represents a linear, saturated hydrocarbon chain comprising from 1 to 12 carbon atoms, even better still from 1 to 4 carbon atoms. Preferably, the group X is chosen from the groups C2H4, C ₃ H ₆ .

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 than or equal to 12, preferably greater than or equal to 14.

More preferably, according to this variant, the compound of general formula 25 (IIA) is chosen from hydrazide derivatives such as the compounds C ₅ Hn-CONHNHCO-C5H11, C9H19-CONH-NHCO-C9H19, CnH ^ -CONH-NHCO-CiiH ^, C ₁₇ H ₃₅ CDNH-NHCO-C17H35, or C ₂ iH4 ₃ -C0NH-N11CO-C2 | H4 ₃ ; ..... diamides such as

N, N'-ethylenedi (laurylamide) of formula ChH ₂₃ -CONH-CH ₂ -CH ₂ -NHCO-CiiH ₃ i, N, N'-ethylenedi (myristylamide) of formula Ci ₃ H ₂ 7-CONH-CH ₂ -CH ₂ -NHCO-Ci ₃ H ₂ 7, 30 N, N'-ethylenedi (paImitamide) of formula Ci ₅ H ₃ i-CONH-CH ₂ -CH ₂ -NHCO-Ci ₅ H ₃ i, N, N'-ethylenedi (stearamide) of formula C1 ₇ H35-CONH-CH2-CH ₂ -NHCO-C1 ₇ H35; mono amides such as laurylamide of formula ChH ₂₃ -CONH ₂ ,

DUPLICATE

19100 Ί 33 - J myristylamide of formula C ₁₃ H ₂ 7- CONH2, palmitamide of formula n C15H31-CONH2, stearamide of formula C17H ₃₅ -CONH ₂ . Even more advantageously, the compound of general formula (IIA) is N, N'- Π ethylenedi (stearamide) of formula C [7H ₃ 5-CONH-CH ₂ -CH ₂ -NHCO-C17H35. ^L 5 Preferably, according to a second variant, the compound of general formula (II) Π is chosen from those of formula (IIB): ^J R2-CONH-R2 '(IIB) Π in which R ₂ and R ₂ ' have the same definition as above. Advantageously, according to this variant, the sum of the numbers of the carbon atoms of R ₂ and R ₂ 'is greater than or equal to 10, advantageously greater than or j equal to 14, of preterence greater than or equal to ai ”. U ^rc ',. ,. carbon of R2 is greater than or equal to 10, advantageously greater than or equal to 12, preferably greater than or equal to 14, and R2 ′ = H. Advantageously, the compound of general formula (II) is chosen from hydrazide derivatives such as the compounds C5HU-CONH-NHCO-C5H11, C9H19-CONHNHCO-C9H19, C11H23-CONH-NHCO-CHH23, C17H35-CONH-NHCO-C17H35, or C21H43-CONH-NHCO-C21H43; diamides such as N, N'ethylenedi (laurylamide) of formula C11H23-CONH-CH ₂ -CH2-NHCO-CnH3i, N, N'J 20 ethylenedi (myristylamide) of formula C] 3H ₂ 7-CONH-CH ₂ -CH ₂ -NHCO-Ci ₃ H ₂ 7, N, N'-ethylenedi (palmitamide) of formula C] 5H3i-CONH-CH2-CH2-NHCO-Ci ₅ H ₃ i, N, N'-ethylenedi (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35; mono amides such as laurylamide of formula C11H23-CONH2, myristylamide [j of formula C13H27-CONH2, palmitamide of formula Cj5H ₃ i-CONH ₂ , stearamide 25 of formula C17H35-CONH2. ..... .......... Even more advantageously, the compound of general formula (II) is N, N'-ethylene di (stearamide) of formula C17H35-CONH-CH2-CH2-NHCO-C17H35. | Preferably, when the chemical additive is chosen from the compounds

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

DUPLICATE

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

(R-NHCO) _X -Z- (NHCO-R ') _y (III), n in which, ^J 5 - R and R', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising heteroatoms

Q 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,

Π 10- Z represents a tri-functionalized group chosen from the groups

------------------------ SüiVâtitS! ------------'----------- -------------------------------------------------- ----------------------------

7 7

MZ ₂ I ^ 3

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

Preferably, when x is 0 and Z represents Z2, the compound of formula (III) is N2, N4, N6-tridecylmelamine having the following formula with R ’representing the group C9H19:

Other preferred compounds corresponding to the formula (ΙΠ), are such that x is equal to 0, Z represents Z2 and R ’represents a saturated hydrocarbon chain, linear, from 1 to

22 carbon atoms, preferably 2 to 18 carbon atoms, preferably 5 to 12 carbon atoms.

DUPLICATE

Other preferred compounds of formula (III) are such as;

y is equal to 0 and Z represents Zj, the compounds then have the formula: j

I r;

O HN ^

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

¹⁰

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

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

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

(IV) with:

- x is an integer,

DUPLICATE

-R is chosen from an alkyl radical in C [-Ci ₂ , alkenyl in C ₂ -Ci ₂ , aryl in Cg-Ci ₂ , or aralkyl in C7-C12, optionally substituted by one or more atoms of halogen, one or several C] -Cg alkoxy groups

According to this variant, the organogelating 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. By this condensation reaction, sorbitol acetals, which are sorbitol derivatives, are obtained. 1,3: 2,4-DÎ-0-benzylidene-D-sorbitol is obtained by reacting 1 mole of D-sorbitol and 2 moles of benzaldehyde and has the formula:

HO

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

OH

HO where Ari and Ar? are optionally substituted aromatic rings.

Among the sorbitol derivatives, other than 1,3: 2,4-Di-O-benzylidene-D-sorbitol, there can be found, for example, 1,3: 2,4: 5,6-tri-O-benzylidene- D-sorbitol, 2,4-mono30 O-benzylidene-D-sorbitol, l, 3: 2,4-bis (p-methylbenzylidene) sorbitol, 1,3: 2,4bis (3,4-dimethylbenzylidene) sorbitol , l, 3: 2,4-bis (p-ethylbenzylidene) sorbitol, l, 3: 2,4-bis (p-propylbenzylidene) sorbitol, l, 3: 2,4-bis (p-butylbenzylidene) sorbitol, l , 3: 2,4-bis (p-ethoxylbenzylidene) sorbitol, l, 3: 2,4-bis (p-chlorobenzylidene) sorbitol,

DUPLICATE

1,3: 2,4-bis (p-bromobenzylideiie) sorbitol, 1,3: 2,4-Di-O-methylbenzylidene-Dsorbitol, 1,3: 2,4-Di-O-dimethylbenzylidene-D-sorbitol, 1,3: 2,4-Di-O- (4methylbenzylidene) -D-sorbitol, 1,3: 2,4-Di-O- (4,3-dimethylbenzylidene) -D-sorbitol.

Preferably, according to this variant, the organogelator compound is 1,3: 2,4-Di-O5 benzylidene-D-sorbitol.

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

Π R ₅ - (COOH) _z (V), ^k in which R5 represents a linear or branched, saturated or unsaturated chain

Π 10 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 varying from 2 to 4.

---------------------- Preferably, the Rj group is a saturated linear chain of formula C _w H2w with w an integer varying from 4 to 22, preferably from 4 to 12.

According to this variant of the invention, the organogelling compounds corresponding to formula (V) can be diacids (z = 2), tracids (z = 3) or tetracids (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 H2 _W -COOH with w an integer varying from 4 to 22, preferably from 4 to 12.

Advantageously, according to this variant, the organogelating 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 1,8octanedioic acid with w = 6, azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9 , 1,2-dodecanedioic acid with w = 10 or tetradecanedioic acid with w = 12.

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

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

DUPLICATE

- - by intermolecular dimerization reaction of at least one unsaturated fatty acid q (Diels Aider reaction 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's to C34,

- ^j 5 in particular in C] 2 to C ₂₂ , in particular in Ci ₆ to C20, and more particularly in C] g.

'I A preferred fatty acid dimer is obtained by dimerization of linoleic acid, ^J thereof can then be partially or fully hydrogenated.

Another preferred fatty acid dimer has the formula HOOC- (CH ₂ ) 7-CH = CH (CH 4 -COOH. Another preferred fatty acid dimer is obtained by dimerization of methyl linoleate. , we can find fatty acid triacids and acid tetracldes gFâs ^ obtained respectively by trimerization ëF □ tetramerisatinn of at least one acirtp orag

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

in which,

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

- (CH ₂ ) q-NH- (CH ₂ ) q- N

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

Among the preferred organogelling compounds corresponding to formula (VI), the following compounds may be mentioned:

DUPLICATE

H ---------------------- Preferably in this variant »the organogelator compound of general formula (VI) is:

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

R-NH-CO-CO-NH-R '(VII) in which, R and R', identical or different, represent a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain, comprising from 1 to 22 carbon atoms, preferably from 8 to 12 carbon atoms, optionally substituted, and optionally comprising heteroatoms, 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 different organogelling compounds of formula (I), (II), (III), (V), (VI) and (VII), the products of reaction of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), in the oil composition.

DUPLICATE η 4ο

i. Advantageously, the coating composition comprises at least one

P organogelling additive chosen from compounds of formula (I), compounds of formula (II) and compounds of formula (V).

P More preferably, the coating composition comprises at least one

L J 5 organogelating additive chosen from compounds of formula (I) or compounds of p formula (V).

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

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

n ί] n

LJ

Li

D f

L <

L.

r ί l.J

Rplnn ifflp prpmiÀrp trarinntp dp r-n tnnrb rlp rAaltcaHnn 1î> pnmpogitinn coating comprises at least one first organogelling compound of formula (V) and at least one second organogelling compound selected from: organogelling compounds of formula (I); the organogelling compounds of formula (II); the organogelling compounds of formula (III); the organogelling compounds of formula (V); organogelling compounds of formula (VI); organogelling compounds of formula (VII) and reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second compound organogelator 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 ( II).

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

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 the 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

DUPLICATE

I) ι

LJ π

η)

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

Advantageously, and according to this first variant, the first 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 a first organogelling compound of formula (II) and at least one second organogelling compound chosen from: organogelling compounds of formula ΠΠ organogelling compounds of formula (II) ; the ------- organogelling compounds of formula (TTI); the organogelling compounds of formula (V); the organogelling compounds of formula (VI); organogelling compounds of formula (VII) and reaction products of at least one C3-C12 polyol and at least one C ₂ -Ci2 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 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 a first organogelling compound of formula (IIA) and at least one second organogelling compound chosen from: organogelling compounds of formula (I); the organogelling compounds of formula (IIB); the organogelling compounds of formula (III); the organogelling compounds of formula (V); organogelling compounds (VI); organogelling compounds of formula 25 (VII) and the reaction products of at least one C3-C12 polyol and at least one C7-C1? aldehyde, in particular those comprising a group of formula (IV), the second organogelling compound being distinct from the first organogelling compound.

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

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

DUPLICATE ^J 19100

Π ⁴²

J When the second organogelling compound is chosen pamii the organogelling compounds of formula (V), it is preferably chosen from acid (j adipic or 1,6-hexanedioic acid with w = 4, pimelic acid or acid 1, 7γί heptanedioic with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, '5 azelaic acid or 1,9-nonanedioic acid with w = 7, sebacic acid or acid p 1, 10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,2J dodecanedioic acid with w - 10 or tetradecanedioic acid with w - 12.

Π According to a third preferred variant of this embodiment, the coating composition ^L comprises at least sebacic acid or 1,10-decanedioic acid

Π 10 and at least N, N ’-ethylenedi (stearamide).

--------------------- According to a fourth feature of this triode deflation, the composition of— £ J ________________ coating comprises at least a first nrganngélatenr of fnrmule Π) and__

U “15

[J

D

Ί 20 at least one second organogelling compound chosen from: organogelling compounds of formula (I); the organogelling compounds of formula (II); the organogelling compounds of formula (III); the organogelling compounds of formula (V); organogelling compounds of formula (VI); the organogelling compounds of formula (VII) and the reaction products of at least one C3-C12 polyol and at least one C2-C12 aldehyde, in particular those comprising a group of formula (IV), the second organogelator compound being distinct from the first organogelling compound.

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

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

J

More preferably, and according to this fourth variant, the second organogelating compound of formula (II) is N, N’-ethÿlènedi (stearamide).

Preferably, and still according to this fourth variant, when the second organogelling compound is chosen from organogelling compounds of formula 30 (V), it is chosen from diacids (ζ = 2), triacids (z = 3) and tetracids (z = 4), preferably from the diacids (z = 2).

Even more preferably, and still according to this fourth variant, the second organogelling compound of formula (V) is chosen from adipic acid or

DUPLICATA 1,6-hexanedioic acid with w = 4, pimelic acid or 1,7heptanedioic acid with w = 5, suberic acid or 1,8-octanedioic acid with w = 6, azelaic acid or acid 1, 9-nonanedioic with w = 7, sebacic or 1,10-decanedioic acid with w = 8, undecanedioic acid with w = 9, 1,25 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 organogelating compound of formula (I) is 2 ’, 3-bis [(3- [3, 5-di-iert ~ butyl-4Π 10 hydroxyphenyl] propionyl)] propionohydrazide.

Preferably, and according to this embodiment, the mass ratio of the first £ J __________________ nrgannoAl atprnr with respect to an rnmpngé. nrganngélatpur is 1: 99 to *,: 1, preferably 1: 9 to 9: 1, still more preferably 1: 5 to 5: 1.

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

Advantageously, the core composition comprises at least one organogelling compound chosen from organogelling compounds of formula (I), the; 20 organogelling compounds of formula (II) and organogelling compounds of formula ^L (V).

More advantageously, the core composition comprises at least one organogelling compound chosen from organogelling compounds of formula (I) and Γ Ί organogelling compounds of formula (V).

Preferably, the core composition comprises at least one compound

I organogelator which is sebacic acid,

- Coating composition

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

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

DUPLICATE

More preferably, the coating composition comprises au. least one organogelating compound chosen from compounds of formula (I), compounds of formula (II) and compounds of formula (V). Even more advantageously, the coating composition comprises at least one organogelating 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-teri-butyl-4-hydroxyphenyl] propionyl)] propionohydrazide, · Γ sebacic acid, 'I and • mixtures of these compounds.

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

Advantageously, when the organogelator compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3, 5-di-teri-butyl-4hydroxyphenyl] propionyl)] propionohydrazide, the composition coating comprises from 0.1% to 5% by mass, preferably from 0.2% to 3.5% by mass of organogelating compound relative to the total mass of the coating composition.

The coating composition includes the oil, the organogelling compound (s) and other additives, if applicable. The other additives can be chosen, for example, from: anti-caking compounds, stickiness dopes, elastomers for bitumen, etc.

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

· 80% to 99.9% by mass of at least one oil chosen from: hydrocarbon oils of petroleum origin or of synthesis, advantageously from hydrocarbon oils of petroleum origin, • 0.1% to 10% by mass, at least one organogelling compound,

DUPLICATE

Γ'Ί I ⁴⁵ . .. i ^LJ 0% to 10% by mass of one or more other additives, i

“1 relative to the total mass of the composition. • i ¹ i

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

ί · 85% to 99.8% by mass of at least one oil, chosen from: oils [

L hydrocarbons of petroleum or synthetic origin, advantageously among oils!

j hydrocarbons of petroleum origin, 0.2% to 5% by mass, of at least one organogelator compound,

Π 10 · 0% to 10% by mass of one or more other additives, u__________________________ ______________________________________ relative to the total mass of the composition.

xi __________________: _______________________________

LJ,

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

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

J 0.5% to 3.5% by mass of at least one organogelator compound, 0% to 10% by mass of one or more other additives relative to the total mass of the composition.

According to a first preferred embodiment, the organogelating compound is chosen from those corresponding to formula (I), in particular 2 ', 3-bis [(3- [3, 5-to-tertbutyl-4-hydroxyphenyl] propionyl) ] propionohydrazide: | i 25 _____________ _____. .. ........ .......... ..... _________ ..... . j

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

· 85% to 99.9% by mass of at least one hydrocarbon oil of petroleum origin, i j 30 · 0.1% to 5% by mass, of at least one organogelating compound of formula (I);

preferably 2 ’, 3-bis [(3- [3, 5-di-to7-butyl-4-i

[| hydroxyphenyl] propionyl)] propionohydrazide ,!

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

U

DUPLICATE

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

Lj 586.5% to 99.8% by mass of at least one original hydrocarbon oil

-n oil,

-J 0.2% to 3.5% by mass, of at least one organogelling compound of formula η (I), advantageously 2 ', 3-bis [(3- [3, 5-di-teri- 4L-butyl hydroxyphenyl] propionyl)] propionohydrazide, n 10 * 0% to 10% by mass of one or more other additives,

------------------------- compared to the total mass of the eôtïipôsitlôfl .--------------- ------------------- 46 relative to the total mass of the composition.

- Process for preparing the coating composition

The coating compositions can be prepared for example according to the following process comprising the steps of:

a) mixing the oil, for example DAO or RAE oil, and heating at a temperature between 140 and 200 ° C, preferably between 150 and 180 ° C, for example from 1 minute to 30 minutes, ’

b) addition of the organogelator compound, mixing and heating at a temperature between 140 and 200 ° C, preferably between 150 and 170 ° C, for example from 10 minutes to 2 hours,

c) optional addition of 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,

d) use in the granule manufacturing process.

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

Γ

L.

- Granule manufacturing process:

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

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

L

DUPLICATA ii) coating the core over 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 of time ranging from 5 minutes to 5 hours, preferably from 5 minutes to 2 hours, iv) optionally, the coating of the granules resulting from step ii) or from step iii), on all or part of their surface, by at least one anti-caking compound.

Preferably, step ii) of application is carried out by dipping, spraying, coextrusion, etc.

Preferably, step iv) of coating the granules is carried out by powdering, sieving, ëîü

[| The shaping of the heart of the granules from an optionally additivated bitumen base can be carried out according to any known process, for example according to the process of

The manufacture described in US 3,026,568, US 4,279,579, WO 2009/153324 or WO 2012/168380. According to a mode of. particular embodiment, the shaping of the core of the solid bitumen can be carried out by _n dewatering, in particular using a drum.

J Other techniques can be used in the solid bitumen core manufacturing process, in particular molding, pelletizing, extrusion ...

i J 20 Preferably, the solid bitumen core particles have a longest average _Γ η dimension ranging from 1 to 30 mm, more preferably 4 to 20 mm, more

L. advantageously from 4 to 15 mm.

p-j Another object of the invention is a bitumen which is solid at room temperature under

Li form of granules obtainable by implementing the process according to the invention as described above. Such a solid bitumen in the form of granules ^u advantageously has the properties described above.

- Uses of solid bitumen granules:

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

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

DUPLICATE ⁴⁸

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

Asphalt mixes are used as materials for the construction and maintenance of pavement bodies and their coating, as well as for carrying out all road works. These include, for example, surface plasters, hot mixes, cold mixes, cold-cast mixes, severe emulsions, base, tie, bonding and rolling coats, and other combinations of 'a bituminous binder and road aggregate having particular properties, such as anti-omiérantes layers, draining mixes, or asphalts p 10 (mixture between a bituminous binder and aggregates of the sand type).

Another object of rinventiüii relates to a method of manufacturing crottëF

D comprising at least one road binder and aggregates, the road binder being chosen from bitumens according to the invention, this process comprising at least the steps of:

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

Q - mixing the aggregates with the road binder in a tank such as a mixer or a mixer drum,

Π n

l]

- obtaining of asphalt.

The method of the invention has the advantage of being able to be carried out without a prior step of heating the granules of solid bitumen.

The mix manufacturing process 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 bitumen that is solid at room temperature melts.

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

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

The solid bitumen 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 room temperature under optimal conditions, in particular without any agglomeration and / or adhesion. solid bitumen during transport and / or

DUPLICATE storage even when ambient temperature is high. In addition, the coating layer of the granules breaks under the effect of contact with the hot aggregates and of shearing and it releases the bitumen base. Finally, the presence of the coating layer in the mixture of road binder and aggregates does not degrade the properties of said road bitumen for road application, compared to an uncoated bitumen base.

U η

L

- Method of transport and / or storage and / or handling of road bitumen

Another object 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 stored and / or handled in a ton of solid bitumen granules at temperature - ------ ambient .------------------------------------------ ----------------------------- Preferably, the road bitumen is transported and / or stored at a high ambient temperature for a longer period or equal to 2 months, preferably greater than or equal to 3 months.

Preferably, the elevated ambient temperature is 20 ° C to 90 ° C, preferably 20 ° C to 80 ° C, more preferably 40 ° C to 80 ° C, even more preferably 40 ° C to 60 ° C .

The bitumen granules according to the invention have the advantage of retaining their divided shape, and therefore of being able to be handled, after storage and / or transport at high ambient temperature. In particular, they have the ability to flow under their own weight without firing, which allows them to be stored in packaging in bags, drums or in containers of all shapes and of all volumes, then to be transferred from this packaging to equipment, as a site equipment (tank, mixer etc ...).

The bitumen granules are preferably transported and / or stored in bulk in bags of 50Û g to 100 kg or 500 kg to 1000 kg commonly called in the field of road bitumens “Big Bag”, said bags being preferably in a thermofusible material. They can 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 different embodiments, variations, preferences and advantages described above for each of the objects of the invention apply to all the objects of the invention and can be taken separately or in combination.

DUPLICATE

The invention is illustrated by the limitative.

• 50 following examples given without

Experimental part :

1. Materials and methods

The rheological and mechanical characteristics of the bitumens to which reference is made in these examples are measured as indicated in Table 1.

Table 1

Π Property Abbreviation Unit Measurement standard i not Needle penetration at 25 ^U C P25 1 / lOimn NF'EN 1426 L1 ball and ring TBA ° C NFEN 1427

The variation in the ball and ring softening temperature (TBA) is measured according to 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 Core composition:

The bitumen base B ₂ is prepared from:

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

.. ......... .- 1,10 decanoic acid (sebacic acid) denoted acid; ......

---------- of the flower of sulfur, noted crosslinking; ------------------------------- ---

- zinc foctanoate; noted scavenger.

The quantities in percentage by mass used for the bitumen base are indicated in Table 2 below.

Table 2

Bitumen b ₂ Bitumen base Bi 98.5%

DUPLICATE

Acid 1.5% SBS - Crosslinking Scavenger P25 (l / 10mm) 14 TBA (° C) 93

Bitumen is prepared as follows.

For bitumen B _2} the bitumen base Bi is introduced into a reactor maintained at ------- 160 ° C with stirring at 300 revolutions / min 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 revolutions / min for 1 hour.

1.2 Coating composition

The coating compositions C | and C ₂ are prepared from:

Oil: A RAE oil was used, that is to say an aromatic oil, marketed by the company TOTAL under the brand Régénis 50 ®.

Organogelling Compounds

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

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

The amounts in percentage by mass used for the preparation of coating compositions C; and C ₂ are shown in Table 3 below.

Table 3

Composition This c ₂ RAE Oil 98.5% 97% Al additive 1.5% 1.5% Addendum A2 - 1.5%

DUPLICATE

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

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

(ii) Adding the organogelling compound (s), and mixing for example 1 5 h 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. Preparation of the various solid bitumen granules Gi

z. 1 General method for the preparation of hearts in Pitume ües granules according to the invention

The B2 bitumen base is heated at 160 ° C for two hours in an oven before being poured into a silicone mold having various spherical shaped holes 15 so as to form the solid bitumen cores. After observing the solidification of the bitumen in the mold, the surplus is leveled with a blade heated with a bunsen burner. After 30 minutes, the solid bitumen in the form of uncoated granules is removed from the mold and stored in a tray covered with silicone paper. The bitumen cores are then allowed to cool to room temperature for 10 to 15 minutes.

2.2 General method for the preparation of the bitumen cores of the granules according to the invention with an industrial process

For the implementation of this method, one can 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 the company.

Sandwik under the trade name of Rotoform.

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

One or more injection nozzles allow (tent) the transfer of the bitumen composition B ₂ inside the double pastillation drum comprising a rotating external drum, the two drums being equipped with slots, nozzles and

DUPLICATE

53

J of orifices allowing the pastillation of drops of bitumen through the first η fixed drum and orifices having a diameter of between 2 and 8 mm of the i-J external rotating drum. The bitumen drops are deposited on the upper face of a horizontal tread driven by rollers.

H 5

P 2.3 General method for coating the core of the granules

The cores of Gj granules obtained above are soaked in one of the

Π liquid coating compositions Ci or C ₂ , prepared previously, then left to dry ^L at room temperature.

n 10 Different coated granules are thus obtained:

- the granules Gf, obtained from the coating composition Ci, and

- Ga ’granules, obtained from 1 a compiasitimn of-coating. C-a ............, .......

3. Evaluation of the behavior of the granules: sticky appearance

The sticky appearance of the granules Gi 'and G ₂ ', prepared previously, is evaluated by touch by a manipulator.

For each type of granule, the handler takes about ten granules and assesses the stickiness of each of them by first placing them between two fingers and then trying to move the fingers away from the surface of the granule.

The results obtained are given in Table 4 below.

Table 4

Granules GT G ₂ ' Sticky appearance + ++

+: little sticky granules, η ++: very little sticky granules.

f The two coating compositions C and C ₂ make it possible to obtain bitumen granules with low stickiness. The coating composition C ₂ , corresponding to the combination i of the two organogelling compounds, makes it possible to obtain even less granules.

L tights.

Claims (15)

DUPLICATE I L Γ ⁵⁴ J CLAIMS l 'J 1. Bitumen which is solid at ambient temperature in the form of granules comprising a core and a coating layer in which: ^J 5 - the core comprises at least one bitumen base, i and J - the coating layer comprises at less: • an oil chosen from a hydrocarbon-based oil of petroleum or synthetic origin, 1 10 “at least one oreanoeelating compound chosen from among the compounds of f general formula (1), (11) or (V): F L. Γ L Γ L f L Arl-Ri-Ar2 (I) j in which: Arl and Ar2 independently of each other represent a benzene ring or a condensed aromatic ring system of 6 to 20 carbon atoms, substituted by at least one group hydroxyl, 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 and ester functions , hydrazide, urea, carbamate, anhydride; R ₂ - (NH) _n CONH- (X) _m - (NHCO) p (NH) _n -R ₂ '(Π) 25 in which: ..... ..... ..... .. ... L. ^J ..... the R groups? and R? '. identical or different, represent r F L. Ί a saturated or unsaturated, linear, branched or cyclic J hydrocarbon chain, comprising from 1 to 22 carbon atoms, optionally substituted, and optionally comprising one or more 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, and R ₂ 'may be H; DUPLICATE 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, C5- hydrocarbon rings 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; such as or R ₅ - (UOOH) _z (V) d ^aT1g -. ^1g q? ^1AllA '..... ................................ ........... ... R5 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 varying 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, in which the hydrocarbon oil is chosen from aromatic oils having an aromatic compound content of between 30 and 95% by mass, advantageously between 50 and 95% by mass, more advantageously. between 60 and 95% by mass relative to the total mass of the aromatic oil. 4.Bitumes, one of the claims, and 2 in which the hydrocarbon oil is selected from paraffinic oils having a total paraffinic compound content of at least 50% by mass based on the total mass of the paraffinic oil. 5. Bitumen according to claim 4, wherein the paraffinic oil has the respective contents: (I) a total content of paraffinic compounds of between 50% and 90%; DUPLICATE (ii) a total content of naphthenic compounds of between 5% and 25%; and (ii) a total content of aromatic compounds of between 5% and 25%, the percentages being expressed by mass relative to the total mass of the paraffinic oil. 6. 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 mass relative to the total mass of the coating layer. U________________________________________ XJ ---------- lû -----. 7. Riturne sekin any one of the preceding claims, wherein 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 mass of organogelating compound relative to the total mass of the coating layer. 15 8. Bitumen according to any one of the preceding claims, in which the core further comprises at least one compound selected from organogelling compounds. 9. Bitumen according to any one of the preceding claims, in which the Q core further comprises at least one pitch having a penetrability at 25 ° C ranging from 0 to 20 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. _.......... 10. A method of manufacturing bitumen according to any of -rj ---------- 25 ----- claims 1 to 9, this method comprising: ----------------------- ----------------- U f] ³⁰ L i) shaping the core from at least one bitumen base, ii) coating the core over all or part of its surface with a coating composition, iii) optionally, drying the granules obtained by 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. DUPLICATE 11. Bituminous mix which comprises a bitumen according to any one of claims 1 to 9 and which further comprises aggregates and optionally mineral and / or synthetic fillers. 12. Bituminous mix according to claim 11 which is a road mix, a bituminous concrete, or a bituminous mastic. 13. A method of manufacturing mixes 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 method comprising at least the steps of: - heating the aggregates to a temperature ranging from 100 ^ü C to 180 ° C, from / 1 ^ 1ΩΟΟΓ ί 1 AQor ......................... .......... ........... .............. - mixing the aggregates with the road binder in a tank such as a mixer or a mixer drum, - obtaining of asphalt. 14. The method of claim 13, which does not include a step of heating the road binder before mixing it with the aggregates. 15. A method of transporting and / or storing bitumen, said bitumen being transported and / or stored in the form of solid bitumen at room temperature according to any one of claims 1 to 9. DUPLICATE LJ ^u 19100 Γ ABRIDGED q Bitumen granules comprising a core and a coating layer in J 5 which: ri - the core includes at least one bitumen base and, LJ - the coating layer includes at least: Π an oil chosen from a hydrocarbon-based oil of petroleum or synthetic ^J origin, Π 10 · at least one organogelating compound chosen from the compounds of general formula (1), (11) or (V). Π ........................................ Process for manufacturing bitumen granules as well as their use as .................... LJ road binder, in particular for the manufacture of asphalt. ü .... 15 Process for the production of mixes from bitumen granules as well as a process for transporting and / or storing and / or handling bitumen granules.