EP2622024A1

EP2622024A1 - Process for the preparation of bituminous mixes and asphalts at low temperatures

Info

Publication number: EP2622024A1
Application number: EP11773881.5A
Authority: EP
Inventors: Laurence Lapalu; Jean-Philippe Paillac; Frédéric Tort; Christian Vermorel
Original assignee: Total Raffinage Marketing SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2010-09-29
Filing date: 2011-09-27
Publication date: 2013-08-07
Also published as: FR2965271B1; BR112013007213A2; WO2012049579A1; FR2965271A1

Abstract

The present invention relates to a process for preparing bituminous mixes and asphalts at lower temperatures. The process involves the mixing of a bituminous binder to which aggregates are added for the bituminous mixes or to which fillers are added for the asphalts, the bituminous binder being added to by means of an additive having the general formula (1): - R₁ and R₂, which are identical or different, represent a hydrogen atom or a polyalkenyl group, a double bond optionally being present between the two carbon atoms bearing the groups R₁ and R₂, - X represents an oxygen atom or a group: - R₃ and R₄, which are identical or different, represent a hydrogen atom or a hydrocarbon-based group containing from 1 to 10 carbon atoms, - R₅ represents a hydrogen atom or a hydrocarbon-based group containing from 1 to 24 carbon atoms, - m represents an integer between 1 and 10, - n represents an integer between 1 and 3, - p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene succinic anhydride, the bituminous binder is free of epoxide resin. This additive of general formula (1) makes it possible to reduce the manufacturing, processing and/or compacting temperatures of the bituminous mixes formulated from said additive-containing bituminous binder and to reduce the manufacturing and/or processing temperatures of asphalts formulated from said additive-containing bituminous binder.

Description

PROCESS FOR THE PREPARATION OF COILS AND LOW ASPHALT

TEMPERATURE

TECHNICAL AREA

The present invention relates to a process for the preparation of asphalt and asphalt at low temperatures. The additivation of an asphalt binder with a particular additive makes it possible to reduce the temperatures of manufacture, of implementation, of compaction of the asphalt mixes and to reduce the temperatures of manufacture and use of the asphalts. The invention also relates to asphalt and asphalt obtained from said process.

The invention also relates to the use of a particular additive in a bituminous binder, to manufacture at lower temperatures asphalt and asphalt.

The invention also relates to the bituminous binder additive with the aid of this particular additive.

The invention finally relates to the use of these asphalts or asphalts for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, floors, waterproofing of buildings or structures , in particular for road applications for the manufacture of foundation layers, base layers, seat layers, surface layers such as tie layers and / or wearing courses.

PRIOR ART

By asphalt is meant a mixture of bituminous binder with mineral fillers. The mineral fillers consist of fines (particles smaller than 0.063 mm), sand (particles with dimensions of between 0.063 mm and 2 mm) and possibly chippings (particles with dimensions larger than 2 mm, preferably between 2 mm and 4 mm).

By bituminous coating is meant a mixture of bituminous binder with aggregates and optionally mineral fillers. The aggregates are inorganic and / or synthetic aggregates, in particular recycling mills with dimensions greater than 2 mm, preferably between 2 mm and 14 mm.

Asphalt is mainly used to make and cover sidewalks, while asphalt is used to make roads. Unlike asphalt, asphalt is not compacted with a roller when it is put in place.

The preparation of hot mixes or asphalts comprises several steps. The first step is to mix the bituminous binder with aggregates (for asphalt mix) or with fillers (for asphalts) at a temperature called manufacturing temperature or coating temperature. The bituminous binder / aggregate mixture or the bituminous binder / filler mixture is then spread (for asphalt) or poured (for asphalt) at a so-called processing temperature. For bituminous mixes, there is then a compaction step at a so-called compaction temperature. After compacting asphalt or pouring asphalt, asphalt or asphalt is cooled to room temperature.

The different temperatures used in the preparation of traditional asphalt and asphalt are very high. Thus, for bituminous mixes, the manufacturing temperature (or coating temperature) and implementation are between 160 ° C and 180 ° C, the compacting temperature is between 120 ° C and 150 ° C. For asphalts these temperatures are even higher, the manufacturing temperatures (or coating temperature) and implementation are between 200 ° C and 250 ° C.

These relatively high temperatures induce high energy costs, greenhouse gas emissions and volatile organic compounds and make working conditions difficult due to radiation and gaseous emissions.

This is why techniques called "cold" have been proposed. These techniques are based on the use of bitumen emulsions, dispersions of bitumen in water. The bitumen emulsions are prepared at temperatures below 100 ° C, but require the use of water and are mainly used for the manufacture of low to medium-stressed pavements because the mechanical performances obtained by these so-called "cold" techniques are generally behind the so-called "hot" techniques.

Another way to lower the preparation temperature of hot mixes and asphalt, are based on so-called "warm" intermediate techniques, techniques that do not involve bitumen emulsions, so that do not involve water, techniques so-called "anhydrous", based on the additivation of the bituminous binder. Various solutions based on the additivation of the bituminous binder have already been proposed.

Thus patent application EP0690102 describes the use of hydrocarbon waxes having a melting point greater than 85 ° C to lower the manufacturing and processing temperatures of the asphaltic products.

WO2004108830 discloses the use of a combination of two additives in a binder to reduce the temperature of manufacture of asphaltic products. The first additive is a hydrocarbon wax whose melting point is greater than 85 ° C. The second additive is a fatty acid ester wax, this wax being of synthetic, plant or fossil plant origin and having a melting point below 85 ° C. The application WO2007135097 describes the use of a combination of two additives in a binder to reduce the temperature of manufacture and / or implementation of an asphaltic or bituminous product. The first additive is a macro-molecular compound chosen from natural resins of vegetable origin or hydrocarbon waxes. The second additive is a fatty acid derivative selected from the group consisting of fatty acid diesters and fatty acid ethers.

The patent application EP2192158 describes the use of at least one fatty acid triglyceride in an asphalt binder to reduce the temperature of manufacture of asphaltic products or hot mixes.

WO2009062925 discloses the use of a combination of additives to prepare warm mixes. The additive combination comprises a surfactant and rheology modifier comprising a wax and a resin.

The patent application EP2062941 describes the use of at least 10% by weight of glycerol in an asphalt binder to reduce the temperature of manufacture of hot mixes.

Moreover, in a completely different field of application, a field which does not aim at reducing the manufacturing temperatures of asphalt or asphalt, it may be noted that patent CN 1232585 discloses an epoxy asphaltic material comprising in particular polyisobutenyl succinic anhydride, an epoxy resin and an accelerator for curing the epoxy resin. The essential element of this asphaltic material is the epoxy resin which reacts in the bituminous mass and makes it possible to obtain an asphaltic material characterized by a high resistance, a high ductility and a very high resistance to wear. To obtain these characteristics, the epoxy resin is indispensable, and the preparation of the material requires a certain amount of reaction so that all of the epoxy resin reacts.

In patent JP4334730, it is a so-called cold technique which involves the use of a bitumen emulsion, the bituminous binder being additive with a reaction product between a polyalkylene polyamine and an alkenylsucinic anhydride and by a polyolefin resin bearing carboxyl groups and having an acid number of between 5 and 100 mg KOH / g. This mixture makes it possible to prepare improved bitumen emulsions.

SUMMARY OF THE INVENTION

In this perspective, the applicant company has sought to find an alternative additive to existing additives, to reduce the manufacturing temperature, implementation and compaction of asphalt and manufacturing temperatures and implementation of asphalt. The applicant company has established, surprisingly, that the preparation of asphalt or asphalt at lower temperatures can be carried out, the preparation process involving a bituminous binder additive with at least one additive of general formula (1) ci -Dessous. The Applicant Company has found that this additive, significantly reduced the temperatures of manufacture, implementation and compaction of asphalt preparation processes and manufacturing temperatures and implementation of asphalt preparation processes. The preparation process according to the invention is an anhydrous type process that does not involve the supply of external water, only the additivation of the binder makes it possible to reduce the manufacturing temperatures.

The processes for preparing the asphalt and asphalt involve the additive of the following general formula (1),

R 1 and R ₂ , which are identical or different, represent a hydrogen atom or a polyalkenyl group, a double bond possibly being present between the two carbon atoms bearing the groups R 1 and R ₂ ,

X represents an oxygen atom or a group:

R ₃ and R 4, which are identical or different, represent a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms,

R ₅ represents a hydrogen atom or a hydrocarbon group of 1 to 24 carbon atoms,

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the process involves a bituminous binder without epoxy resin. In the general formula (1), when X represents a group: the nitrogen atom is of course in the ring between the two carbons carrying the carbonyl groups, the linkage with the ring is via the nitrogen atom.

This additive has the advantage of being used alone and not in admixture or combination with other additives, as is the case in the prior art. Moreover this additive is inexpensive, easily available and not labeled.

The main objective of the present invention is therefore to provide a process for the preparation of asphalt and asphalt cast at lower temperatures, in order to reduce energy consumption, to reduce the discharge of combustion gases and to reduce emissions. fumes.

For asphalt mixes, the objective is to prepare so-called "warm" mixes and to reach a coating temperature of 100 ° C. to 150 ° C., preferably of 110 ° C. to 140 ° C., more preferably of 120 ° C. C at 130 ° C, an operating temperature of 80 ° C to 130 ° C, preferably 90 ° C to 120 ° C, more preferably 100 ° C to 1 10 ° C, and / or a temperature of compacting from 70 ° C to 120 ° C, preferably from 80 ° C to 110 ° C, more preferably from 90 ° C to 100 ° C.

For asphalts, the objective is to achieve a coating temperature of 140 ° C to 180 ° C and / or an operating temperature of 120 ° C to 160 ° C.

Another object of the present invention is to provide a process for preparing asphalt and asphalt cast at lower temperatures, which is economical because implementing a low additive content.

Another object of the present invention is to provide a process for preparing bituminous mixes and asphalts at lower temperatures, in which the properties of the additive-containing binder are not modified or slightly modified with respect to the non-additive base bitumen. Thus the properties such as the consistency (penetrability, Ball and Ring temperature) or the viscosity of the additive binder must not be modified.

Another object of the present invention is to provide a process for the preparation of asphalt and asphalt cast at lower temperatures, to ensure good adhesiveness bituminous binder additive / aggregates and allowing a low stripping.

Another object of the present invention is to provide a process for the preparation of asphalt and asphalt cast at lower temperatures which is anhydrous.

Another object of the present invention is to provide a process for the preparation of asphalt and asphalt cast at lower temperatures, the asphalt or asphalt obtained by said process having equivalent or improved mechanical properties compared with traditional asphalt and asphalt. , conventionally manufactured from known processes at higher temperatures. In particular, one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to stripping.

In particular, one of the objectives of the present invention is to provide a warm mix produced at lower temperatures, having good resistance to rutting.

In particular, one of the objectives of the present invention is to provide a warm mix manufactured at lower temperatures, having a good modulus of rigidity.

In particular, one of the objectives of the present invention is to provide an asphalt manufactured at a lower temperature having the required indentation and shrinkage values.

BRIEF DESCRIPTION

The invention relates to a process for the preparation of a bituminous mix in which a bituminous binder is mixed with aggregates, the bituminous binder comprising at least one bitumen and at least one additive of general formula (1) in which:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, the coating temperature of said bituminous binder and aggregates being between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 140 ° C .; ° C and 130 ° C, being understood when the additive of general formula (1) is a polyisobutylene succinic anhydride, the bituminous binder is free of epoxy resin.

Preferably, the bituminous binder and the granulates are both at a temperature of between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C., when 'coating.

Preferably, the processing temperature during the spraying of the bituminous binder / granulate mixture is between 80 ° C. and 130 ° C., preferably between 90 ° C. and 120 ° C., more preferably between 100 ° C. and 110 ° C. .

Preferably, the compacting temperature of the spilled mixture is between 70 ° C. and 120 ° C., preferably between 80 ° C. and 110 ° C., more preferably between 90 ° C. and 100 ° C.

The invention also relates to a method for preparing an asphalt in which a bituminous binder is mixed with fillers, the bituminous binder comprising at least one bitumen and at least one additive of general formula (1) in which:

X represents an oxygen atom or a group:

R ₃ and R ₄ , which are identical or different, represent a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms,

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, the manufacturing temperature being between 140 ° C. and 180 ° C., preferably between 150 ° C. and 170 ° C., it being understood that when the additive of general formula (1 ) is a polyisobutylene succinic anhydride, the bituminous binder is free of epoxy resin. Preferably, the bituminous binder and the fillers are both at a temperature between 140 ° C and 180 ° C, preferably between 150 ° C and 170 ° C, when mixed.

Preferably, the operating temperature during the pouring of the bituminous binder / filler mixture is between 120 ° C. and 160 ° C., preferably between 130 ° C. and 150 ° C.

Preferably, the bituminous binder is free of epoxy resin.

Preferably, the bituminous binder comprises from 0.1 to 20% by weight of additive of formula (1), relative to the weight of bituminous binder, preferably from 0.5 to 10% by weight, more preferably from 1 to at 5% by weight.

Preferably, the polyalkenyl group is a polyolefinic group chosen from polyethylenes, polypropylenes and polybutenes, such as polyisobutenes.

Preferably, the polyalkenyl group has a weight average molecular weight of between 100 and 100,000, preferably between 200 and 50,000, more preferably between 500 and 10,000, even more preferably between 1,000 and 5,000.

In a preferred embodiment, in the general formula (1), R 1 represents a polyisobutene group, R ₂ represents a hydrogen atom, X represents an oxygen atom and there is no double bond between the two carbon atoms. carbon bearing groups Ri and R ₂ .

In another preferred embodiment, in the general formula (1), R 1 represents a polyisobutene group, R ₂ represents a hydrogen atom and X represents a group with:

R ₃ , R 4 and R ₅ represent a hydrogen atom,

p is 0,

n is 1,

m is equal to 4, and there is no double bond between the two carbon atoms carrying the groups R 1 and R ₂ .

In another preferred embodiment, in the general formula (1), R 1 and R ₂ represent a hydrogen atom, X represents a group with: R 3 and R ₄ represent a hydrogen atom,

R ₅ represents a hydrocarbon group of 1 to 22 carbon atoms,

p is 0,

n is 1,

m is equal to 1, a double bond is present between the two carbon atoms carrying the groups R 1 and R ₂ .

Preferably, the bituminous binder further comprises a polymer.

Preferably, the bituminous binder further comprises a crosslinking agent.

The invention also relates to a bituminous mix obtainable by the process as defined above.

The invention also relates to an asphalt that can be obtained by the process as defined above.

The invention also relates to the use of an additive of general formula (1) in a bituminous binder comprising at least one bitumen, for reducing the temperatures of manufacture, of implementation and / or of compacting during the preparation of an asphalt b the general (1) being, with:

X represents an oxygen atom or a roule:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3, p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the bituminous binder is free of epoxy resin.

The invention also relates to the use of an additive of general formula (1) in a bituminous binder comprising at least one bitumen, for reducing the temperatures of manufacture and / or implementation during the preparation of an asphalt, the additive of general formula (1) being with:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the bituminous binder is free of epoxy resin.

The invention also relates to a bituminous binder comprising at least one bitumen and at least one additive of general formula (1):

(1) R 1 and R ₂ , which are identical or different, represent a hydrogen atom or a polyalkenyl group, a double bond possibly being present between the two carbon atoms bearing the groups R 1 and R ₂ ,

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, it being understood that the bituminous binder is free of epoxy resin or of polyolefin resin bearing carboxyl groups and having an acid number of between 5 and 100 mg KOH / g, and it being understood that the groups R 1 and R ₂ are not simultaneously hydrogen atoms when X is an oxygen atom.

The invention also relates to a process for the preparation of a bituminous binder as defined above, in which the mixing temperature of the bitumen of the additive of general formula (1) is between 100 ° C. and 170 ° C. preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 130 ° C.

The invention finally relates to the use of asphalt or asphalt as defined above, for the manufacture of pavements of roads, pavements, sidewalks, roads, urban developments, soils, d sealing of buildings or structures, in particular for the manufacture in road application, of foundation layers, base layers, base layers, surface layers such as tie layers and / or layers of rolling.

DETAILED DESCRIPTION

The process for the preparation of asphalt mixes or asphalts according to the invention uses at least one bitumen, said bitumen comprising at least one additive of general formula (1) with:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the process involves a bituminous binder without epoxy resin.

Preferably, the process for preparing the asphalt or asphalt involves a bituminous binder free of epoxy resin.

Preferably, the process for preparing the mixes or asphalts involves a bituminous binder free of polyolefin resin bearing carboxyl groups and having an acid number of between 5 and 100 mg KOH / g.

By polyolefin resin bearing carboxyl groups and having an acid number of between 5 and 100 mg KOH / g means oxidized polyethylene waxes, oxidized polypropylene waxes, ethylene / acrylic acid copolymers, ethylene / methacrylic acid, ethylene / maleic acid copolymers (maleic anhydride), propylene / maleic acid copolymers (maleic anhydride), ethylene / itaconic acid copolymers (itaconic anhydride). This resin, just like the epoxy resin, is not necessary for the process according to the invention. It is possible to prepare an asphalt or asphalt at lower temperatures without both types of resin, thanks only to the additive of general formula (1). The additives binders, and asphalt and asphalt obtained from these additives binders, have good properties (consistency, viscosity, adhesiveness, modulus, rutting ...) even without these two types of resin.

Preferably, the method of preparation of the asphalt or asphalt involves a bituminous binder free of maleic anhydride, that is to say that the groups R 1 and R ₂ are not simultaneously hydrogen atoms when X is a oxygen atom. The presence of maleic anhydride, if maleic anhydride there is, is in the form of traces and is due to an incomplete reaction between the reagents involved to prepare the additive of general formula (1). The amount of free maleic anhydride is less than 1% by weight, relative to the amount of bituminous binder, preferably less than 0.5%, more preferably less than 0.2%, even more preferentially less than 0.1% by weight. %, even more preferably less than 0.01%.

The term "polyalkenyl group" or "polyolefinic group" means a group derived from the polymerization of olefinic units (olefins or alkenes). Suitable olefins are olefins of 2 to 10 carbon atoms such as ethylene, propylene, n-butene, isobutene, n-hexene, n-octene-1, methyl-2-heptene 1, propyl-2-propyl-5-hexene-1. The polyalkenyl group may therefore be a polyethylene, polypropylene, polybutene or a polybutene mixture, polyisobutylene (also called polyisobutene) being preferred.

The polyalkenyl group is therefore not constituted by a single olefinic unit, but by at least 2 olefinic units having previously been polymerized with each other.

Preferably, the polyalkenyl group comprises from 2 to 50 olefinic units, preferably from 5 to 40, more preferably from 10 to 20. The polyalkenyl group is therefore an exclusively hydrocarbon group consisting solely of carbon and hydrogen atoms.

Preferably, the polyalkenyl group is derived from the polymerization of the same olefinic unit, preferably from the polymerization of isobutylene.

The number-average molecular mass M _n of the polyalkenyl group is between 50 and 5,000, preferably between 100 and 25,000, more preferably between 250 and 5,000, even more preferably between 500 and 2,500, even more preferably between 600 and 2,500. 2000, even more preferably between 750 and 1500, still more preferably between 900 and 1500.

The weight average molecular weight M _w of the polyalkenyl group is between 100 and 100 000, preferably between 200 and 50 000, more preferably between 500 and 10 000, even more preferably between 1000 and 5000, still more preferably between 1200 and 5000. and 4000, even more preferably between 1500 and 3000, even more preferably between 1800 and 2000. These molecular masses are measured by GPC chromatography with a polystyrene standard according to ASTM D3536 (replaced by ASTM D5296-05).

The polyalkenyl group mainly comprises α-olefins and in a minor way β-olefins. Preferably, the polyalkenyl group comprises more 60% by weight of α-olefins, relative to the mass of the polyalkenyl group, more preferably more than 70% by weight, still more preferably more than 80% by weight, more preferably more than 90% by weight . Traces of tetrasubstituted olefins may also be present. It will be less than 5% by weight, relative to the mass of the polyalkenyl group, preferably less than 3%, more preferably less than 1%.

The polyalkenyl group has a polydispersity index M _w / M _n between 1 and 4, preferably between 1, 2 and 3, more preferably between 1.5 and 2, even more preferably between 1, 6 and 1.8.

The polyalkenyl group has a number of bromine measured according to the ASTM D 1 1 59 standard of between 5 and 50, preferably between 10 and 30, more preferably between 15 and 20.

The polyalkenyl group has a viscosity number measured according to the standard IS 0 2909, between 80 and 300, preferably between 100 and 250, more preferably between 150 and 200.

In the general formula (1), when X represents an oxygen atom, the additive has the general formula (la) in which R 1 and R ₂ , which are identical or different, are as defined above. , in particular with regard to the definitions and characteristics given for the polyalkenyl group, a double bond possibly being present between the two carbon atoms carrying the groups Ri and R ₂ :

Preferably, in the general formula (Ia), R 1 and R ₂ are different, R 1 represents a polyalkenyl group as defined above and R ₂ represents a hydrogen atom.

Preferably, in the general formula (Ia), there is no double bond between the two carbon atoms carrying the groups R 1 and R ₂ .

Preferably, the additive of general formula (Ia) is a reaction product between a polyalkenyl group and maleic anhydride.

Preferably, in the general formula (Ia), the polyalkenyl group is a polyisobutene group. Preferably, the additive of general formula (Ia) is, for example, a reaction product between polyisobutylene and maleic anhydride, the reaction scheme of which is as follows:

Step 1

Polyisobutylene of monosubstituted succinic anhydride

In this first step, during the reaction, for example between the polyisobutene group and maleic anhydride, the major compound that is formed is a polyisobutylene monosubstituted succinic anhydride. The quantity of polyisobutylene monosubstituted succinic anhydride is greater than 50% by weight, relative to the amount of total product obtained, preferably greater than 60%, more preferably greater than 70%>, still more preferably greater than 80%>, even more preferably greater than 90%>.

It is also possible to have some polyisobutylene of disubstituted succinic anhydride. The amount of polyisobutylene of disubstituted succinic anhydride is less than 30% by weight, relative to the amount of total product obtained, preferably less than 20%, more preferably less than 10%, even more preferentially less than 5%, more preferably less than 2%.

There are also traces of free maleic anhydride. The amount of free maleic anhydride is less than 5% by weight, relative to the amount of total product obtained, preferably less than 2%, more preferably less than P / 0, more preferably less than 0.5%> .

There are also traces of unreacted polyisobutylene. The amount of unreacted polyisobutylene is less than 15% by weight, relative to the amount of total product obtained, preferably less than 10%, more preferably less than 5%, even more preferably less than 2%. more preferably less than 1%.

The additive of general formula (Ia) is preferably a polyisobutylene of succinic anhydride. The apolar part of the polyisobutylene group undoubtedly makes it possible to compatibilize the additive with the bitumen and the polar part of the cyclic imide undoubtedly allows a good affinity of the additive with the aggregates.

In the general formula (1), when X represents a group, with:

R ₅ represents a hydrogen atom or a hydrocarbon group of 1 to

24 carbon atoms,

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, the additive has for general formula the following general formula (Ib) with:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, in which R 1 and R ₂ , which are identical or different, are as defined above, in particular with regard to the definitions and characteristics given for the polyalkenyl group, a double bond possibly being present between the two carbon atoms carrying the groups R 1 and R ₂ .

Preferably, R 3 and R ₄ , which may be identical or different, represent a hydrogen atom or a hydrocarbon group of 2 to 8 carbon atoms, more preferably 4 to 6 carbon atoms.

Preferably, R ₅ represents a hydrogen atom or a hydrocarbon group of 2 to 22 carbon atoms, more preferably 4 to 20, even more preferably 8 to 18, even more preferentially 10 to 16, even more preferably 12 to 14. .

Preferably, m is an integer between 2 and 8, more preferably between 3 and 6, even more preferably between 4 and 5.

Preferably, n is an integer between 1 and 2.

Preferably in the general formula (Ib), R 1 and R ₂ are different, one being a hydrogen atom and the other a polyalkenyl group as defined above.

Preferably, there is no double bond between the two carbon atoms bearing the groups R 1 and R ₂ .

Preferably, the additive of general formula (Ib) is a reaction product obtained in two steps, the first step involving a polyalkenyl group as defined above and maleic anhydride (step 1 described above in relation with the additive of general formula (la)), followed by a reaction with an amine of the following general formula (2) with R 3, R ₄ , R 5, m, n and p which have the definitions given above:

Polyamines of general formula (2) that may be used according to the invention are, for example, polyalkyleneamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentam and their substituted derivatives. The tetraethylenepentam is the preferred polyalkyleneamine, then p is 0, n is 1, m is 4, R ₃ , R 4 and R 5 are identical and represent a hydrogen atom.

Polyamines of general formula (2) which can be used according to the invention are also N-alkylpolylkylenepolyamines such as N-alkylethylenediamines, N-alkylpropylenediamines, N-alkylbutylenediamines, N-alkyldiethylenetriamines, N-alkyldipropylenetriamines, N-alkyldibutylenetriamines, N-alkyltriethylenetetramines, N-alkyltripropylenetetramines and N-alkyltributylenetetramines, the alkyl radical being the R ₅ group, a hydrocarbon group of 1 to 22 carbon atoms, preferably of 4 to 18 carbon atoms, more preferably of 8 to 16 carbon atoms, and even more preferably from 10 to 12 carbon atoms. N-tallowpropylenediamine is the preferred N-alkylpolylkylenepolyamine.

Preferably, in the general formula (Ib), the polyalkenyl group is a polyisobutene group.

Preferably, the additive of general formula (Ib) is for example a reaction product between a polyisobutylene succinic anhydride and tetraethylenepentam amine of general formula (2) preferred, the reaction scheme is as follows:

Polyisobutylene of monosubstituted succinic anhydride

2nd step

Reaction product in cyclic imide form

Reaction product in bis-imide form In this second step, during the reaction, for example, between the monosubstituted succinic anhydride polyisobutylene and the tetraethylenepentamine, the compound which is formed is predominantly in the form of a cyclic imide. There may be product in the form of an amide, product of opening of the imide ring.

The amount of imide form is greater than 50% by weight, relative to the imide form / amide form, preferably greater than 60%, more preferably greater than 70%>, still more preferably greater than 80%). more preferably greater than 90%>. One can also have the formation of a bis-imide.

Preferably, the additive of general formula (Ib) is a reaction product between polyisobutylene succinic anhydride and tetraethylenepentamine. The apolar portion of the polyisobutylene group probably allows the compatibilization of the additive with the bitumen and the polar portion provided by the amine undoubtedly allows a good affinity of the additive with the aggregates.

In the general formula (1), there is therefore a single polyalkenyl group for a maleic anhydride unit for the particular additive (la) when X is an oxygen atom, and a single polyalkenyl group for the particular additive (lb). ) when X is the group:

The additive of general formula (Ia) is obtained by reaction between 1 mole of the polyalkenyl group and 1 mole of maleic anhydride. The additive of general formula (Ib) is obtained by reaction of 1 mole of additive of general formula (Ia) with 1 mole of amine of general formula (2). The additive of general formula (1) is thus distinguished, for example, from maleic anhydride grafted polyolefins, in which several units of maleic anhydride for a polyolefin chain are found.

When in the additive of general formula (Ib), a double bond is present between the two carbon atoms bearing the groups R 1 and R ₂ , the additive has the following general formula:

wherein R 1, R ₂ , R ₃ , R 4, R 5, n 1, n and p are as defined above. Preferably, R 1 and R ₂ are identical and are preferably hydrogen atoms. In this case, the additive of general formula (Ic) is, for example, a reaction product between maleic anhydride and an amine of the following general formula (2) with R ₃ , R 4, R 5, n, n and p which have the definitions given above:

The preferred additive of the general formula (Ic) is a maleimide of n-tallow propylene diamine, a reaction product between maleic anhydride and N-tallow propylenediamine. The apolar part of the R ₅ group probably allows the compatibility of the additive with the bitumen and the polar part provided by the amine undoubtedly allows a good affinity of the additive with the aggregates.

The process according to the invention uses an amount of additive of general formula (1) in bitumen of between 0.1 and 20% by weight of additive of general formula (1), relative to the mass of binder. bituminous, preferably between 0.5 and 10% by weight, more preferably between 1 and 5% by weight, more preferably between 1 and 2% by weight.

It is preferred to use the smallest amount of additive possible, for economic reasons, but also technical. Indeed, if the additive is present in a large quantity in the bituminous binder, the properties of the bituminous binder such as penetrability, ball and ring temperature, viscosity, adhesiveness, complex modulus and properties of the bituminous mix. obtained from said bituminous binder such as Duriez resistance, rut resistance and modulus, may be affected and become too far from those of the non-additive binder and the coating obtained from said non-additive binder.

Preferably, the process uses an amount of additive of general formula (1) of from 0.1 to 2% by weight, based on the weight of bituminous binder, preferably from 0.5 to 1.5%, more preferably from 0.7 to 1%.

The additive of general formula (1) is essential to the process according to the invention and makes it possible to prepare asphalts and asphalts at lower manufacturing, processing and compacting temperatures and at very low levels in the bituminous binder. This additive allows a very good adhesiveness and wettability of the bituminous binder vis-à-vis the aggregates, the bituminous binder is very manageable, even at lower temperatures than those traditionally implemented.

The additive of general formula (1) is introduced into the bitumen, in pure form (that is to say as such) or diluted in an oil. This oil can be synthetic or of mineral or vegetable origin or a combination of all three. This oil does not evaporate and its presence does not modify the properties of the final bituminous binder. The percentage of oil may be between 0 and 50% of the oil-additive mixture of general formula (1), and preferably between 20 and 50%.

The method according to the invention also implements at least one bitumen. This bitumen is taken alone or mixed. Among the bitumens that can be used according to the invention, mention may be made first of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or oil sands. The bitumens according to the invention are also bitumens derived from the refining of crude oil. Bitumens come from the atmospheric and / or vacuum distillation of oil. These bitumens can be optionally blown, vis-reduced and / or deasphalted. The different bitumens obtained by the refining processes can be combined with one another to obtain the best technical compromise. Bitumen can also be a recycling bitumen. The bitumens may be hard grade or soft grade bitumens. The bitumens according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, between 5 and 200 1/10 mm, preferably between 10 and 100 1/10 mm, more preferably between 20 and 60 1 / 10 mm, even more preferably between 30 and 50 1/10 mm.

The method according to the invention can also implement at least one polymer. The polymers used are elastomers or plastomers. For example, thermoplastic elastomers such as random or block copolymers of styrene and butadiene, linear or star (SBR, SBS) or styrene and isoprene (SIS), copolymers which may be mentioned in an indicative and nonlimiting manner, include ethylene and vinyl acetate, copolymers of ethylene and propene, terpolymers of ethylene / propylene / diethylene (EPDM), terpolymers of acrylonitrile / butadiene / styrene (ABS ), olefin homopolymers and copolymers of ethylene (or propylene, or butylene), polyisobutylenes, polybutadienes, polyisoprenes, polyvinyl chloride, rubber crumbs, butyl rubbers, polychloroprenes, polynorbornenes, polybutenes, polyisobutenes, polyethylenes or any polymer used for the modification of bitumens and mixtures thereof.

Preferred polymers are copolymers of styrene and butadiene. The styrene-butadiene copolymer advantageously has a weight content of styrene ranging from 5% to 50% by weight, based on the weight of the copolymer, preferably from 20% to 40% by weight.

The styrene-butadiene copolymer advantageously has a weight content of butadiene, ranging from 50% to 95% by weight, based on the weight of the copolymer, preferably from 60% to 80% by weight.

Among the butadiene units, the 1-4-double-butadiene units derived from butadiene and the 1-2-double-butadiene units derived from butadiene are distinguished. By reasons to 1-4 double bonds derived from butadiene means the units obtained via a 1,4-addition during the polymerization of butadiene. 1,2-Butadiene double-bonded units are understood to mean the units obtained via a 1,2-addition during the polymerization of butadiene. The result of this addition 1,2 is a so-called "pendant" vinyl double bond.

The copolymer of styrene and butadiene has a content of 1,2-butadiene-derived double-bonded units of between 5% and 50% by weight, based on the total weight of the butadiene units, preferably between 10% and 40%>, more preferably between 15% and 30%, even more preferably between 20% and 25% o, still more preferably between 18%> and 23%>.

The styrene-butadiene hydrocarbon copolymer has an average molecular weight Mw of between 4,000 and 500,000 daltons, preferably between 10,000 and 200,000, more preferably between 50,000 and 150,000, even more preferably between 80,000 and 10,000. and 130,000, even more preferably between 100,000 and 120,000. The molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to ASTM D3536 (replaced by ASTM D5296-05).

The styrene-butadiene copolymer may be linear or starred, diblock, triblock and / or multi-branched. The styrene-butadiene hydrocarbon copolymer may also optionally include a statistical hinge. A mixture of copolymers of styrene and butadiene may be envisaged.

In general, a quantity of polymer of 1 to 20% by weight relative to the mass of bituminous binder is used, preferably from 5 to 10%, more preferably from 2 to 4%.

This polymer may optionally be crosslinked. The crosslinking agents that can be used are of a very varied nature and are chosen as a function of the type (s) of polymer (s) contained in the bituminous binder according to the invention. Preferably, the crosslinking agent is selected from sulfur alone or in admixture with vulcanization accelerators. These vulcanization accelerators are either hydrocarbyl polysulfides, sulfur-donor vulcanization accelerators, or non-sulfur donor vulcanization accelerators. The hydrocarbyl polysulfides may be chosen from those defined in the patent FR2528439. The sulfur-donor vulcanization accelerators may be chosen from thiuram polysulfides, for example, tetrabutylthiuram disulfides, tetraethylthiuram disulfides and tetramethylthiuram disulfides. The non-sulfur-donor vulcanization accelerators that may be used according to the invention may be selected sulfur compounds, in particular among mercaptobenzothiazole and its derivatives, dithiocarbamates and its derivatives, and monosulfides of thiuram and its derivatives. For example, zinc-2-mercaptobenzothiazole, zinc dibutyldithiocarbamate and tetramethylthiuram monosulphide may be mentioned. For more details on the sulfur-donor and non-sulfur-donor vulcanization accelerators that can be used according to the invention, reference can be made to patents EP0360656, EP0409683 and FR2528439. In general, an amount of crosslinking agent of 0.05 to 2% by weight relative to the mass of bituminous binder is used, preferably from 0.1 to 1%, even more preferably from 0.2 to 0.5.

The process according to the invention can also use fluxing agents such as oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin. The oils of animal and / or vegetable origin may be in the form of free fatty acids, triglycerides, diglycerides, monoglycerides, in esterified form, for example in the form of methyl ester.

The process according to the invention can also use waxes of animal, plant or hydrocarbon origin, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or Fischer-Trospch waxes. Polyethylene waxes or Fischer-Trospch waxes may optionally be oxidized. Amide waxes such as ethylene bis-stearamide may also be added.

The method according to the invention can also implement resins of plant origin such as rosins.

The process according to the invention can also use acids such as polyphosphoric acid or diacids, in particular fatty diacids.

The method can also implement adhesiveness dopes and / or surfactants. They are chosen from alkylamine derivatives, alkyl-polyamine derivatives, alkylamidopolyamine derivatives, alkyl amidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture. The most used are the tallow propylene diamines, the tallow amido amines, the quaternary ammoniums obtained by quaternization of tallow propylene diamines, the tallow propylene-polyamines.

It is also possible to add sorbitol derivatives, hydrazide derivatives and imidazolidinone derivatives.

By using the additive of the general formula (1) as described above, the process for the preparation of the mixes and the asphalts is carried out at lower temperatures than those conventionally used. This is known as a process for preparing "warm" and not "hot" bituminous mixes.

The process for preparing the mixes is characterized in that the mixing or coating of the aggregates with the bituminous binder additive is done at a particularly low temperature, the coating temperature or manufacture of the mix being between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C.

During the coating, the aggregates and the additive-containing bituminous binder are either both at the same temperature between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C, the bituminous binder additive is at a temperature around 160 ° C and the aggregates are at a temperature between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C C and 130 ° C. Due to the large amount of aggregates relative to the bituminous binder additive (approximately 95% by weight of aggregates with respect to 5% by weight of bituminous binder additive), it is the temperature of the aggregates which dictates the overall temperature of the aggregate. coating which will therefore be between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C.

It is preferred to use the aggregates at the temperature between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. and 130 ° C. and the bituminous binder additive at the same temperature between 100 ° C. C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C.

Since the additive bituminous binder with the additive of general formula (1) does not affect the viscosity of the bituminous binder and does not reduce it, when the viscosity of the bituminous binder is too high to allow the pumping of the bituminous binder, it is then preferred to use the bituminous binder additive at 160 ° C and the aggregates at a temperature between 100 ° C and 150 ° C, preferably between 1 10 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C ° C, the overall coating temperature is still between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C. In this case, the additivated bituminous binder is preferably at a temperature between 120 ° C and 180 ° C, preferably between 140 ° C and 160 ° C and the aggregates at a temperature between 100 ° C and 150 ° C, preferably between 1 10 ° C and 140 ° C, more preferably between 120 ° C and 130 ° C, the overall coating temperature is always between 100 ° C and 150 ° C, preferably between 1 10 ° C and 140 ° C ° C, more preferably between 120 ° C and 130 ° C.

Although the coating temperature is lower in the process according to the invention, the coating is of good quality and the coating time is not increased compared to a traditional process at higher temperature. Thus the coating time of the process according to the invention is between 2 seconds and 30 minutes, preferably between 5 seconds and 20 minutes, more preferably between 10 seconds and 10 minutes, even more preferably between 20 seconds and 5 minutes. minutes, even more preferably between 30 seconds and 1 minute. It is preferable that the mixing time or coating time be as short as possible to avoid the formation of fines and the change of distribution of the aggregates. In any case, it is not necessary to have longer coating times in the present invention and it is even sought that they be as short as possible.

Once the aggregates are coated, the additive bituminous binder / aggregate mixture is widespread. The application temperature during spreading of the bituminous binder / granulate mixture is between 80 ° C. and 130 ° C., preferably between 90 ° C. and 120 ° C., more preferably between 100 ° C. and 110 ° C. The whole is then compacted and the compaction temperature of the mixture spread is between 70 ° C and 120 ° C, preferably between 80 ° C and 1 10 ° C, more preferably between 90 ° C and 100 ° C. The whole is then cooled to room temperature.

The invention also relates to bituminous mixes obtained by said process, said mixes comprising a bituminous binder, aggregates and optionally fillers. The bituminous mix comprises from 1 to 10% by weight of bituminous binder additive, relative to the total mass of the mix, preferably from 4 to 8% by weight.

The process for preparing cast asphalts is characterized in that the mixture of the fillers with the binder is at a particularly low temperature, the asphalt manufacturing temperature being between 140 ° C. and 180 ° C., preferably between 150 ° C and 170 ° C. It should be noted that during manufacture, the fillers and the additive bituminous binder are both at the same temperature (between 140 ° C. and 180 ° C., preferably between 150 ° C. and 170 ° C.). Then, the bituminous binder / additive mixture is poured. The operating temperature during the pouring of the bituminous binder / filler mixture is between 120 ° C. and 160 ° C., preferably between 130 ° C. and 150 ° C. The whole is then cooled to room temperature.

Another subject of the invention is cast asphalts obtained by said process, said asphalts comprising a bituminous binder and mineral fillers. The asphalt comprises from 1 to 20% by weight of bituminous binder additive, relative to the total mass of the asphalt, preferably from 5 to 10% by weight.

The subject of the invention is also the use in a bitumen of at least one additive of general formula 1) with:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the bituminous binder is free of epoxy resin, in order to reduce the temperatures of manufacture, implementation and / or compaction of bituminous mixes and the temperatures of manufacture and / or implementation of cast asphalts.

The use of this additive makes it possible to lower the said temperatures of all bitumens (hard grade bitumens, intermediate grade bitumens, soft grade bitumens), irrespective of their penetrability. Thus the additive is suitable for penetration bitumens of between 35 and 50 1/10 mm and penetration bitumens of between 10 and 20 1/10 mm.

This additive of general formula (1) makes it possible to lower said temperatures while preserving the mechanical properties of bituminous mixes and cast asphalts, and at very low levels of additives.

The use of the additive of general formula (1), during the manufacture of an asphalt mix, makes it possible to obtain manufacturing or coating temperatures between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C, more preferably between 120 ° C and 130 ° C. The use of the additive of general formula (1) makes it possible to obtain application temperatures during spreading between 80 ° C. and 130 ° C., preferably between 90 ° C. and 120 ° C., more preferably between 100 ° C and 1 10 ° C. The use of the additive of general formula (1) makes it possible to obtain compacting temperatures between 70 ° C. and 120 ° C., preferably between 80 ° C. and 110 ° C., more preferably between 90 ° C. and 100 ° C.

The use of the additive of general formula (1), during the manufacture of an asphalt, makes it possible to obtain manufacturing temperatures between 140 ° C. and 180 ° C., preferably between 150 ° C and 170 ° C. The use of the additive of general formula (1) makes it possible to obtain operating temperatures between 120 ° C. and 160 ° C., preferably between 130 ° C. and 150 ° C.

The use of the additive of general formula (1), during the manufacture of a mix, makes it possible to reduce the manufacturing temperatures from 10 ° C. to 80 ° C., preferably from 20 ° C. to 60 ° C., more preferably from 30 ° C to 50 ° C. The use of the additive of general formula (1) makes it possible to reduce the temperatures of implementation during spreading from 30 ° C. to 100 ° C., preferably from 40 ° C. to 120 ° C., more preferably 50 ° C. C at 70 ° C. The use of the additive of general formula (1) makes it possible to reduce the compaction temperatures from 30 ° C. to 80 ° C., preferably from 40 ° C. to 70 ° C., more preferably from 50 ° C. to 60 ° C.

The invention also relates to the use of asphalt mixes and poured asphalts according to the invention for the manufacture of road, pavement, sidewalk, road, urban development, soil, waterproofing of buildings or structures, in particular for the manufacture in road application, of foundation layers, base layers, foundation layers, surface layers such as bonding layers and / or wearing courses .

The invention finally relates to a bituminous binder additive with at least one additive of general formula (1):

X represents an oxygen atom or a roule:

m represents an integer between 1 and 10, n represents an integer between 1 and 3,

The subject of the invention is also the process for preparing the additivated bituminous binder as defined above, in which at least one bitumen and at least one additive of general formula (1) are mixed at a temperature of between 100 ° C. and 170 ° C, preferably between 110 ° C and 150 ° C, more preferably between 120 ° C and 130 ° C. The mixing time is between 10 minutes and 4 hours, preferably between 30 minutes and 3 hours, more preferably between 1 hour and 2 hours.

EXAMPLES

The different products used are the following:

- a pure bitumen having a penetration of 41 1/10 mm (according to the standard EN1426) and a ball and ring temperature of 51.4 ° C (according to standard EN 1427),

an additive of general formula (1) denoted Ai which is a polyisobutylene of succinic anhydride with:

R 1 is a polyisobutylene group of molar mass around 1000 g ^/ mol ^-1 , with a polydispersity index equal to 1.6, comprising 88% by weight of α-olefin, 6% by weight of β-olefin and 1 5% by weight of tetrasubstituted olefin ( ¹³ C NMR), the bromine number of which is 17 (ASTM D 1159) and the viscosity number of which is 140 (ISO 2909),

R ₂ is a hydrogen atom,

there is no double bond between the two carbon atoms carrying the groups Ri and R ₂ and,

X is an oxygen atom, this additive Al is a reaction product between polyisobutylene having the characteristics given above and maleic anhydride,

an additive of general formula (1) denoted A ₂ which is a maleimide of n-tallow propylene diamine with:

Ri and R ₂ are hydrogen atoms,

there is a double bond between the two carbon atoms carrying the groups Ri and R ₂ ,

- X is a group with

R3 and R4 are hydrogen atoms,

R ₅ is a hydrocarbon group of 16 to 18 carbon atoms, m, n and p are 1, this additive is a reaction product between maleic anhydride and n-tallow propylene diamine,

an additive of general formula (1) denoted A ₃ which is a polyisobutylene succinimide with:

R 1 is a polyisobutylene group of molar mass around 1000 g ^/ mol ^-1 , with a polydispersity index equal to 1.6, comprising 88% by weight of α-olefin, 6% by weight of β-olefin and 1.5% by weight of tetrasubstituted olefin ( ¹³ C NMR), the bromine number of which is 17 (ASTM D 1159) and the viscosity number of which is 140 (ISO 2909),

R ₂ is a hydrogen atom,

there is no double bond between the two carbon atoms carrying the groups Ri and R ₂ ,

- X is a group - CHR ₄ -VNR ₅ - H ^WITH:

R ₃ , R 4 and R ₅ are hydrogen atoms,

p is 0,

n is 1,

m is 4, this additive is a reaction product between polyisobutylene having the characteristics given above and maleic anhydride, followed by a reaction with tetraethylenepentamine.

Various bituminous binders are prepared:

The bituminous binder Lo is a control bituminous binder not comprising any additive according to the invention. The bituminous binder Lo consists of the pure bitumen described above.

Li bituminous binder is a bituminous binder according to the invention additive with the additive A1 described above. The bituminous binder Li comprises 99% by weight of pure bitumen as defined above and 1% by weight of additive Al.

- The bituminous binder L ₂ is a bituminous binder according to the invention additive with the additive A ₂ described above. The bituminous binder L ₂ comprises 99% by weight of pure bitumen as defined above and 1% by mass of additive A ₂ .

- The bituminous binder L ₃ is a bituminous binder according to the invention additive with the additive A ₃ described above. The bituminous binder L ₃ comprises 99% by weight of pure bitumen as defined above and 1% by weight of additive A3.

Preparing bituminous binders L _ls L ₂ and L ₃ by mixing the binder Lo respectively and the additive Ai, A ₂ or A ₃ at a temperature of 120 ° C. Table 1: Properties of bituminous binders

Penetration P ₂₅ measured at 25 ° C according to EN 1426.

Ball and ring temperature measured according to EN standard

Penetration index (or Pfeiffer index).

w Viscosity at 160 ° C, 140 ° C and 120 ° C measured according to standard NF EN 12596.

Passive adhesiveness measured according to standard PR NF EN 15626.

Complex module E * measured according to standard NF EN 14770.

It is found that the bituminous binders according to the invention Li to L ₃ have properties equivalent to those of the bituminous binder L ₀ in terms of penetrability, ball and ring temperature, plasticity range, adhesiveness and complex modulus .

It is found that the additivation of the bituminous binders according to the invention Li to L ₃ does not degrade the properties of the bituminous binders according to the invention Li to L ₃ .

The adhesiveness is even improved for the bituminous binders according to the invention Li to L ₃ . It is noted in particular that the additive does not affect the viscosity of the binder, does not reduce the viscosity of the binder, the viscosities at 120 ° C., 140 ° C. and 160 ° C. of the bituminous binders according to the invention Li to L ₃ are comparable to those of the control bituminous Lo. The additive of general formula (1) allows the reduction of the manufacturing temperatures despite an unchanged viscosity.

Then prepared various asphalt E _0, E ₀ _bis, E _ls E ₂ and E ₃ from 5.4% by weight binders respectively L _0, L _0, L _ls L ₂ and L ₃ and aggregates The Noubleau type containing 35% by mass of sand 0-2, 9.5% by weight of aggregates 2-4, 11.4% by mass of aggregates 4-6, 36.9% by mass of aggregates 6-10 and

1, 9%) by weight of filler.

The bituminous control mix Eo is prepared at the manufacturing temperature or coating temperature of 165 ° C., the aggregates and the bituminous binder Lo being all both at 165 ° C for 37 seconds. The bituminous binder / aggregate mixture is then spilled at 155 ° C, compacted at 145 ° C and cooled to room temperature

The Eobis bituminous control mix is prepared at the manufacturing temperature or coating temperature of 120 ° C., the aggregates and the bituminous binder Lo being both at a temperature of 120 ° C. for 70 seconds. The bituminous binder / aggregate mixture is then spilled at 100 ° C, compacted at 80 ° C and cooled to room temperature.

- The bituminous mix according to the invention Ei is prepared at the manufacturing temperature or coating temperature of 120 ° C, the aggregates and the bituminous binder

Li being both at a temperature of 120 ° C for 64 seconds. The bituminous binder / aggregate mixture is then spilled at 100 ° C, compacted at 80 ° C and cooled to room temperature.

- The bituminous mix according to the invention E ₂ is prepared at the manufacturing temperature or coating temperature of 120 ° C, the aggregates and the bituminous binder

L ₂ being both at a temperature of 120 ° C for 61 seconds. The bituminous binder / aggregate mixture is then spilled at 100 ° C, compacted at 80 ° C and cooled to room temperature.

- The bituminous mix according to the invention E ₃ is prepared at the manufacturing temperature or coating temperature of 120 ° C, the aggregates and the bituminous binder

L ₃ being both at a temperature of 120 ° C for 56 seconds. The bituminous binder / aggregate mixture is then spilled at 100 ° C, compacted at 80 ° C and cooled to room temperature.

The mixing times expressed in seconds correspond to the mixing time required between the binder and the aggregates so that all the aggregates are covered with binder.

It is found that the mixing time is very short when the unadditive binder Lo and the aggregates are heated at high temperature (coated Eo prepared at 165 ° C). When the temperature of the binder L ₀ and the aggregates at 120 ° C. are reduced, the mixing time increases enormously, from 37 seconds to 70 seconds for the coating E ₀ bi _s . This mixing time is reduced when the bituminous binder is additive with the additives according to the invention, as evidenced by the mixing times of the mixes E ₁ to E ₃ . It is therefore possible to prepare warm mixes at 120 ° C without increasing the mixing time and without degrading the properties of bituminous mixes. Table 2: Properties of bituminous mixes

Water stripping resistance test according to standard NF P 98-251-1, reflects the adhesion between the bituminous binder and the aggregates.

Rutting resistance test according to standard NF EN 12697-22, reflects the capacity of the bituminous mix to resist creep related to the application of the traffic.

It is observed that the asphalt according to the invention E ₃ has a resistance to stripping, identical to that of the coated bituminous witness E _0, but with a lower production temperature of 45 ° C, a bottom temperature of implementation 55 ° C and a compacting temperature lower than 65 ° C.

It is found that the bituminous mix according to the invention E ₃ has a resistance to rutting, identical to that of the bituminous mix Eo control, but with a manufacturing temperature lower than 45 ° C, a temperature of implementation 55 ° C lower and a lower compaction temperature of 65 ° C.

It can therefore be concluded that the additivation, at low additive contents, of the bituminous mix according to the invention E ₃ makes it possible to reduce the manufacturing, coating and compacting temperatures of the mixes without degrading the mechanical properties of the bituminous mixes. .

Claims

A process for the preparation of a bituminous mix in which a bituminous binder is mixed with aggregates, the bituminous binder comprising at least one bitumen and at least one additive of general formula (1) in which:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, the coating temperature of said bituminous binder and aggregates being between 100 ° C. and 150 ° C., preferably between 110 ° C. and 140 ° C., more preferably between 120 ° C. C. and 130 ° C., it being understood that when the additive of general formula (1) is a polyisobutylene of succinic anhydride, the bituminous binder is free of epoxy resin.

The process for preparing a bituminous mix according to claim 1, wherein the bituminous binder and the granules are both at a temperature of between 100 ° C and 150 ° C, preferably between 110 ° C and 140 ° C. more preferably between 120 ° C and 130 ° C, during the coating.

3. Process for the preparation of a bituminous mix according to claim 1 or 2, in which the application temperature during spreading of the bituminous binder / aggregate mixture is between 80 ° C. and 130 ° C., preferably between 90 ° C. C and 120 ° C, more preferably between 100 ° C and 110 ° C. A process for the preparation of a bituminous mix according to any one of claims 1 to 3, wherein the compaction temperature of the spilled mixture is between 70 ° C and 120 ° C, preferably between 80 ° C and 110 ° C more preferably between 90 ° C and 100 ° C.

A method of preparing an asphalt in which a bituminous binder is mixed with fillers, the bituminous binder comprising at least one bitumen and at least one additive of the general formula (1) in which:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

p represents an integer equal to 0 or 1, the manufacturing temperature being between 140 ° C. and 180 ° C., preferably between 150 ° C. and 170 ° C., it being understood that when the additive of general formula (1 ) is a polyisobutylene succinic anhydride, the bituminous binder is free of epoxy resin.

The method of preparing an asphalt according to claim 5, wherein the bituminous binder and the fillers are both at a temperature between 140 ° C and 180 ° C, preferably between 150 ° C and 170 ° C, when of their mixture.

A method of preparing an asphalt according to claim 5 or 6, wherein the application temperature during casting of the bituminous binder / filler mixture is between 120 ° C and 160 ° C, preferably between

130 ° C and 150 ° C.

8. Process for the preparation of a bituminous mix or asphalt according to any one of claims 1 to 7 wherein the bituminous binder is free of epoxy resin.

9. Process for the preparation of an asphalt mix or asphalt according to any one of claims 1 to 8, in which the bituminous binder comprises from 0.1 to 20% by weight of additive of formula (1), by relative to the mass of bituminous binder, preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight.

10. A process for preparing a bituminous mix or asphalt according to any one of claims 1 to 9 wherein the polyalkenyl group is a polyolefinic group selected from polyethylenes, polypropylenes, polybutenes such as polyisobutenes.

11. A process for preparing an asphalt mix or asphalt according to any one of claims 1 to 10 wherein the polyalkenyl group has a weight average molecular weight of between 100 and 100,000, preferably between 200 and 50 000, more preferably between 500 and 10 000, even more preferably between 1000 and 5000.

12. Process for the preparation of a bituminous mix or asphalt according to any one of claims 1 to 1 1 wherein R 1 represents a polyisobutene group, R ₂ represents a hydrogen atom, X represents an oxygen atom. and there is no double bond between the two carbon atoms carrying the groups R 1 and R ₂ .

13. A process for the preparation of a bituminous mix or asphalt according to any one of claims 1 to 1 1 wherein R 1 represents a polyisobutene group, R ₂ represents a hydrogen atom and X represents a group with:

p is 0,

n is 1,

m is equal to 4, there is no double bond between the two carbon atoms carrying the groups R 1 and R ₂ .

14. Process for the preparation of a bituminous mix or asphalt according to any one of claims 1 to 1 1 wherein R 1 and R ₂ represent a hydrogen atom, X represents a group with: N r rCHR ₃ (CH ₂ ) _p CHR ₄ TNR ₅ T-H

- R ₃ and P represent a hydrogen atom,

R ₅ represents a hydrocarbon group of 1 to 22 carbon atoms,

p is 0,

n is 1,

15. A process for preparing an asphalt or asphalt mix according to any one of claims 1 to 14 wherein the bituminous binder further comprises a polymer.

16. The process for preparing an asphalt or asphalt mix according to any one of claims 1 to 15 wherein the bituminous binder further comprises a crosslinking agent.

17. A bituminous coating obtainable by the process according to any one of claims 1 to 4 and 8 to 16.

18. Asphalt obtainable by the process according to any one of claims 5 to 16.

19. Use of an additive of general formula (1) in a bituminous binder comprising at least one bitumen, for reducing the temperatures of manufacture, implementation and / or compaction during the preparation of an asphalt mix, additive of the general formula (1) being with:

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

20. Use of an additive of general formula (1) in an asphalt binder comprising at least one bitumen, for reducing the temperatures of manufacture and / or implementation during the preparation of an asphalt, the additive of formula general (1) being, with:

X represents an oxygen atom or a roule:

m represents an integer between 1 and 10,

21. Bituminous binder comprising at least one bitumen and at least one additive of general formula (1):

X represents an oxygen atom or a group:

m represents an integer between 1 and 10,

n represents an integer between 1 and 3,

22. A process for the preparation of a bituminous binder according to claim 21, wherein the mixing temperature of the bitumen of the additive of general formula (1) is between 100 ° C and 170 ° C, preferably between 10 ° C and 170 ° C. ° C and 150 ° C, more preferably between 120 ° C and 130 ° C.

23. Use of an asphalt mix according to claim 17 or an asphalt according to claim 18, for the manufacture of road, pavement, sidewalk, road, urban development, soil, watertightness, roadway and roadway surfacing. buildings or works, in particular for the manufacture under road application, of foundation layers, basecoats, foundation layers, surface layers such as tie layers and / or wearing courses.