OA18634A - Composition bitume / polymère présentant des propriétés mécaniques améliorées. - Google Patents

Abstract

Composition bitume/polymère thermo-réticulable à base d'au moins un élastomère de type S-B1-B2, avec S un polymère styrénique ou autre vinylaromatique, B1 et B2 des polybutadiènes, la composition comprenant un adjuvant de type polymère oléfinique, la composition ayant des propriétés mécaniques améliorées. Utilisation de ces compositions dans les domaines des applications routières telles que les enrobés à chaud ; les enrobés tièdes ; les enrobés à froid par exemple les enrobés coulés à froid ou les graves émulsions ; ou les enduits superficiels, par exemple les émulsions ou les bitumes fluxés ; et dans les domaines des applications industrielles, par exemple dans la fabrication de revêtements intérieurs et extérieurs.

Description

BITUMEN / POLYMER COMPOSITION PRESENTING IMPROVED MECHANICAL PROPERTIES

Technical area

The present invention relates to the field of bitumens. More specifically, it relates to heat-crosslinkable bitumen / polymer compositions comprising an adjuvant of olefinic polymer type, these compositions having improved mechanical properties.

The invention also relates to the use of these compositions in the fields of road applications such as hot mix; lukewarm mixes; cold mixes, for example cold mixes or severe emulsions; or surface coatings, for example emulsions or fluxed bitumens; and in the fields of industrial applications, for example in the manufacture of interior and exterior coatings.

State of the prior art

Much work has focused on improving the mechanical, elastic and / or rheological properties of bituminous compositions. Bitumen / polymer compositions exhibiting improved properties as well as their preparation process have been widely described in the literature.

Among the polymers added to bitumens, random or block copolymers of styrene and a conjugated diene and, in particular, of styrene and butadiene or of styrene and isoprene are known to be particularly effective because they mix very easily in bitumens and give them excellent mechanical properties and in particular very good elastic properties.

These bitumen / polymer compositions are used for the preparation of binders for coatings of various surfaces and, in particular, as road surface coatings, provided that these compositions in combination exhibit a certain number of mechanical characteristics. Optimized mechanical characteristics such as elastic properties are particularly crucial for applications in road surfaces.

Application WO97 / 43341 describes bitumen / polymer compositions containing a bitumen or a mixture of bitumens and 0.3% to 20%, by weight relative to the weight of bitumen, of at least one primary polymer chosen from certain elastomers and 35 plastomers and 0.01% to 12% by weight of at least one adjuvant of olefinic polymer type bearing epoxy or COOH groups. The polymers used in this document are different from those of the invention. The role of the adjuvant is

DUPLICATE to avoid demixing between the bituminous phase and the polymer phase, which improves the storage stability of the composition.

Application WO2015 / 071370 describes bitumen / polymer compositions exhibiting improved cold mechanical properties and comprising:

- a first bitumen base having an intrinsic stability S greater than 2.5 and / or a peptization rate Sa greater than 0.60

- a second bitumen base having an intrinsic stability S less than or equal to 2.50 and / or a peptization rate Sa less than or equal to 0.60,

- an elastomer and,

- an olefinic polymer adjuvant functionalized with at least glycidyl functional groups.

The compositions illustrated are crosslinked with sulfur and use an SBS block terpolymer.

Application WO2008 / 137394 describes a process for preparing a bituminous binder composition modified with a polymer in the absence of crosslinking agents by heating a bitumen to a temperature of 160 ° C. to 221 ° C., adding a block copolymer composition and agitation to form a homogeneous mixture. The block copolymer compositions used comprise one or more block copolymers having at least one monovinylaromatic block, at least one polybutadiene block having a vinyl content of less than 15 mol percent and at least one polybutadiene block having a vinyl content of more of 25 percent by moles. It is taught that the bitumen / polymer compositions thus formulated have improved mechanical properties, such as ductility, and good storage stability.

However, it was found that the mechanical properties of some of these compositions were not entirely satisfactory, in particular it was found that the tensile strength of these compositions was generally insufficient.

It has also been found that the storage stability of some of these compositions is not entirely satisfactory.

The invention aimed to develop an additivated bitumen composition which is heat-crosslinkable and which exhibits elastic properties and improved storage stability. We sought a system which is effective in all kinds of bitumens and which is not limited to an application to very specific bitumens. It has been sought to develop compositions exhibiting improved tensile strength and satisfactory storage stability.

Summary of the invention

The invention relates to a bitumen / polymer composition comprising:

DUPLICATE

I। - bitumen,

- at least one elastomer, and

- at least one olefinic polymer adjuvant functionalized with at least glycidyl functional groups, characterized in that:

• the elastomer is chosen from heat-crosslinkable block copolymers of formula S-B1-B2, in which S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, Bl is a polybutadiene block having a content of vinyl less than or equal to 15 mole percent, 10 B2 is a polybutadiene block having a vinyl content of greater than or equal to 25 mole percent, the B1 / B2 mass ratio is greater than or equal to 1: 1, and in wherein the SB 1 -B2 block copolymer has a peak molecular weight of 40,000 to 200,000;

• the elastomer can also comprise at least one heat-crosslinkable block copolymer corresponding to the formula (S-B1-B2) nX in which each S 15 represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, each B 1 represents a polybutadiene block having a vinyl content of less than or equal to 15 mole percent, each B2 represents a polybutadiene block having a vinyl content of greater than or equal to 25 mole percent, n is an integer ranging from 2 to 6, and X is the residue of a coupling agent, in which the weight ratio B1 / B2 is greater than or equal to 1: 1, and the block copolymer (S-B1-B2) nX has a weight peak molecular weight which is 1.5 to 6.0 times the peak molecular weight of the S-B1-B2 block copolymer;

and the elastomer / adjuvant mass ratio in the composition ranges from 15/1 to 2 / l.

A subject of the invention is also a process for preparing a bitumen / polymer composition as defined above, and below for the preferred embodiments, characterized in that it is brought into contact, by operating at temperatures between 100 ° C and 200 ° C and with stirring for a period of at least 10 minutes:

- bitumen,

- from 0.5% to 20% by mass of at least one elastomer,

- from 0.05% to 2.5% by mass of at least one olefinic polymeric adjuvant, - optionally additives.

According to a preferred embodiment, the mass ratio:

S-B1-B2 / (S-Bl-B2) nX

DUPLICATE is greater than or equal to 1: 1, preferably 1: 1 to 10: 1, and more preferably 1: 1 to 4: 1.

According to a preferred embodiment, S represents styrene. 5

According to a preferred embodiment, the composition comprises from 0.5% to 20% by mass of elastomer relative to the total mass of the composition, preferably from 0.5 to 15%.

According to a preferred embodiment, the composition comprises from 0.05% to

2.5% by mass of olefinic polymeric adjuvant relative to the total mass of the composition, preferably from 0.15 to 2%.

According to a preferred embodiment, the olefinic polymer builder is selected from the group consisting of:

(a) copolymers, random or block, of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by mass of ethylene;

(b) terpolymers, random or block, of ethylene, of a monomer A selected from vinyl acetate and C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer selected from acrylate of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed of units from ethylene; and (c) the copolymers resulting from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, on a substrate consisting of a polymer chosen from polyethylenes, polypropylenes, random or block copolymers of ethylene and vinyl acetate and random or block copolymers of ethylene and of C 1 to C ₆ alkyl acrylate or methacrylate, comprising from 40% to 99.7% by weight of ethylene, said graft copolymers comprising of 0.5% to 15% by mass of grafted units derived from monomer B, (d) mixtures of at least two compounds (a), (b) and (c).

DUPLICATE

According to an advantageous embodiment, the olefinic polymer adjuvant is chosen from random or block terpolymers of ethylene, of a monomer A chosen from vinyl acetate and alkyl acrylates or methacrylates in C | at C6 and a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by mass of units derived from monomer A and from 0.5% to 15% by mass of units derived from monomer B, the remainder being formed of units derived from ethylene.

According to an even more advantageous embodiment, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene, of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.

The invention also relates to an asphalt characterized in that it comprises at least one bitumen / polymer composition as defined above, and mineral and / or synthetic fillers.

The invention also relates to an asphalt characterized in that it consists essentially of at least one bitumen / polymer composition as defined above, and mineral and / or synthetic fillers.

The invention also relates to a bituminous mix characterized in that it comprises at least one bitumen / polymer composition as defined above, aggregates, and optionally mineral and / or synthetic fillers.

The invention also relates to a bituminous mix characterized in that it consists essentially of at least one bitumen / polymer composition as defined above, aggregates, and optionally mineral and / or synthetic fillers.

DUPLICATE

The invention also relates to the use of at least one bitumen / polymer composition as defined above for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold mix, a serious emulsion, said binder being associated with aggregates and / or recycling mills.

The invention also relates to the use of at least one bitumen / polymer composition as defined above, to prepare a waterproofing coating, a membrane or an impregnation layer.

The compositions of the invention have many advantages: they have improved elastic properties, in particular improved tensile strength, in particular tensile strength at 5 ° C measured according to standard EN 13587 greater than or equal to 500%. They also exhibit satisfactory hot storage stability, in particular storage stability at 180 ° C greater than or equal to 15 to 3 days, in particular storage stability at 180 ° C characterized by a variation in penetrability at 25 ° C measured according to EN 1426 standard less than or equal to 5 1/10 mm and / or a Ball and Ring temperature variation measured according to standard 1427 less than or equal to 5 ° C. The developed combination of elastomer and olefinic polymer builder improves the mechanical properties, including elastic properties, and storage stability of a wide variety of bitumen compositions.

detailed description

The Applicant has discovered that the use of a specific elastomer in combination with a particular polymer adjuvant for the preparation of bitumen / polymer compositions makes it possible to surprisingly improve the mechanical properties, in particular the elastic properties, in particular resistance to water. the traction, and the storage stability of this bitumen / polymer composition. Indeed, the Applicant has demonstrated a particular synergistic effect induced by the joint use of a particular elastomer and of a specific polymer adjuvant. This observation is not limited to any particular class of bitumens.

In addition, the bitumen / polymer composition of the invention has the advantage of being economical compared to a bitumen / polymer composition based on the same S-B1-B2 block polymers and without adjuvant. Indeed, the addition of the adjuvant, in low

DUPLICATA quantity, makes it possible to significantly reduce the quantity of block polymer used, with equivalent or even better mechanical properties, and makes it possible to obtain very satisfactory storage stability.

In the present invention, the expression "bitumen / polymer composition" and "bitumen / polymer binder" represent the same type of composition and are used interchangeably.

The expression "consists essentially of" followed by one or more characteristics, means that may 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 significantly modify the properties and characteristics of the invention.

Bitumens:

The invention relates to bitumens. These can be formed by one or more bitumen bases.

By "bitumen" is meant any bituminous compositions consisting of one or more bitumen bases and optionally comprising one or more chemical additives, said compositions being intended for road application or industrial application.

Among the bitumen bases that can be used according to the invention, there may be mentioned first of all bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or tar sands and bitumens from the refining of crude oil . The bitumen bases according to the invention are advantageously chosen from bitumen bases obtained from the refining of crude oil. The bitumen bases can be chosen from bitumen bases or mixtures of bitumen bases originating from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches. Bitumen bases can be obtained by conventional processes for manufacturing bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumen bases can optionally be vis-reduced and / or deasphalted and / or air-rectified. It is common practice to perform vacuum distillation of atmospheric residues from atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feed supplying the vacuum distillation corresponding to the atmospheric residues. These vacuum residues from the vacuum distillation tower can also be DUPLICATED as bitumens. It is also common to inject air into a feed usually composed of distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This process makes it possible to obtain a base which is blown, or semi-blown or oxidized 5 or air-rectified or partially air-rectified.

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

According to the invention, for the conventional methods of manufacturing bitumen bases, the operation is carried out at manufacturing temperatures of between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, and with stirring for a period of d 'at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours. The term “production temperature” is understood to mean the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and duration of 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 as a function of the properties targeted for the blown bitumen and as a function of the quality of the starting bitumen.

Bitumen can also be recycled bitumen.

The bitumens can be hard grade or soft grade bitumens. The bitumens which can be used according to the invention have a penetrability, measured at 25 ° C. according to standard EN 1426, of 5 to 330 1/10 mm, preferably between 10 to 220 1/10 mm, more preferably from 10 to 120 1. / 10 mm.

As is well known, the so-called "needle penetrability" measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C (P25). This characteristic

DUPLICATE of penetrability is expressed in tenths of a millimeter (dmm or l / ΊΟ mm). The needle penetrability, measured at 25 ° C, according to the standardized test NF EN 1426, represents the measurement of the penetration in a bitumen sample, after a time of 5 seconds, of a needle whose weight with its support is 100 g. The 5 standard NF EN 1426 replaces the approved standard NF T 66-004 of December 1986 with effect from December 20, 1999 (decision of the Director General of AFNOR dated November 20, 1999).

The olefinic polymer builder

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, (d) mixtures of these copolymers.

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

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

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

Monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.

The ethylene / monomer A / monomer B terpolymers comprise from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0 5% to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene;

(c) the copolymers result from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, onto a polymer substrate. The polymer substrate consists of a polymer chosen from polyethylenes, in particular

DUPLICATE

ΙΟ 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 acrylate or methacrylate C1-C6 alkyl comprising from 40% to 99.7% by weight, preferably from 50% to 99% by weight of ethylene. Said graft copolymers comprise from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of grafted units obtained from monomer B.

(d) The olefinic polymer builder may consist of a mixture of two or more copolymers selected from categories (a), (b) and (c).

The olefinic polymer adjuvant is preferably chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from mixtures (d) comprising them.

The olefinic polymer adjuvant is advantageously chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from the mixtures (d) in which the terpolymers (b) represent at least 50% by mass. relative to the total mass of the mixture, preferably at least 75% by mass, even better still at least 90% by mass.

Advantageously, the olefinic polymer adjuvant is chosen from random terpolymers of ethylene, of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen from glycidyl acrylate 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 weight, preferably 2.5% to 15% by weight, of units derived from monomer B, the remainder being formed from units derived from ethylene.

The elastomer:

The elastomer is a triblock copolymer or a mixture of triblock copolymers.

It is selected from heat-crosslinkable block copolymers of formula S-B1-B2, in which S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, B1 is a polybutadiene block having a vinyl content of less than or equal at 15 mole percent, B2 is a polybutadiene block having | a vinyl content of 25 mole percent or more, and the ratio of

DUPLICATE mass B1 / B2 is greater than or equal to 1: 1, and wherein the S-B1B2 block terpolymer has a peak molecular weight of from about 40,000 to about 200,000.

The elastomer may further comprise at least one heat-crosslinkable block copolymer corresponding to the formula (S-B1-B2) nX in which each S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, each B1 represents a polybutadiene block having a vinyl content less than or equal to 15 mole percent, each B2 represents a polybutadiene block having a vinyl content greater than or equal to 25 mole percent, n is an integer ranging from 2 to 6 , and X is the residue of a coupling agent, the B1 / B2 mass ratio is greater than or equal to 1: 1, and the block copolymer (S-B1B2) nX has a peak molecular weight which is 1, 5 to 6.0 times the peak molecular weight of S-B1-B2 block copolymer.

The monovinylaromatic hydrocarbon groups designated S can be any monovinylaromatic hydrocarbon compound known for use in the preparation of block copolymers such as: styrene, Γο-methylstyrene, pmethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof. The preferred monovinyl aromatic hydrocarbon compound according to the present invention is styrene, which is used as a substantially pure monomer or as a major component in mixtures with minor proportions of another structurally related vinyl aromatic monomer, such as 'o-methylstyrene, pmethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely in proportions of not more than 10% by weight . The use of substantially pure styrene is particularly preferred in the present invention.

The blocks of polybutadiene B1, B2 entering into the composition of the block copolymers mentioned above are based on butadiene monomer which is practically pure or comprising minor proportions, up to 10% by weight, of structurally related conjugated dienes. Preferably, the polybutadiene is purely constituted from butadiene monomer.

With respect to the block copolymers of the present invention, the term molecular weight refers to the actual molecular weight in g / mole of the block copolymer. The molecular weights mentioned in the description and claims can be measured by gel permeation chromatography (GPC) using polystyrene standards, for example as taught according to ASTM 3536. GPC is a well known method in which polymers are separated according to their molecular mass, with the larger molecule eluting first.

DUPLICATE

The chromatograph is calibrated using commercially available polystyrene standards of various molecular weights. The molecular mass of polymers measured by GPC is a molecular mass in equivalents of styrene. The equivalent molecular weight of styrene can be converted to the true molecular weight when the styrene content of the polymer and the vinyl content of the diene blocks are known. The detector used is preferably a combination of ultraviolet rays and a refractive index detector. Molecular masses are measured at the top of the peak of CPG, converted to true molecular masses, and are commonly referred to as "peak molecular masses".

The peak molecular weight of each monovinyl aromatic hydrocarbon block, in particular of polystyrene, is from about 10,000 to about 25,000, preferably from about 12,000 to about 20,000. According to a preferred variant, the peak molecular weight of the Styrenic blocks ranges from about 14,000 to about 18,000.

Each block copolymer of formula S-B1-B2 used in the present invention has a peak molecular weight of from about 40,000 to about 200,000, preferably from about 65,000 to about 160,000, more preferably from about 75,000 to about 150,000, and still more preferably about 75,000 to 130,000.

The peak molecular weight of the block copolymers of formula (S-B1-B2) nX depends on the peak molecular weight of the block copolymer of the formula S-B1-B2 used. More specifically, the peak molecular weight of the (S-B1B2) nX copolymers is from about 1.5 to about 6.0 times the peak molecular weight of the S-B1-B2 block copolymer. Preferably, the peak molecular weight of the (S-B1-B2) nX block copolymers is from about 1.8 to about 5.0 times the peak molecular weight of the S-B1-B2 block copolymer.

The combined molecular mass of the two butadiene blocks (B1 and B2) is about 25,000 to about 190,000. The two butadiene blocks (B1 and B2) are present in a B1 / B2 weight ratio greater than or equal to 1: 1. In other words, B1 is present in an amount (% by weight) greater than or equal to 50% of the total of segment B1-B2 and B2 is present in an amount (% by weight) less than or equal to 50% of the total of segment B1-B2.

When 1,3-butadiene is polymerized through a 1,2-addition mechanism, the result is a vinyl group hanging from the backbone of the polymer. As noted above, polybutadiene is present in blocks or segments which contain varying levels of vinyl. This vinyl content allows the polymer to be characterized.

Regarding the B1 polybutadiene block, it is preferred that there is at most about 15 mole percent vinyl in the B1 block.

DUPLICATE

Preferably, the vinyl content in the B1 block should be from about 5 mole percent to about 15 mole percent of the condensed polybutadiene units. Based on known anionic polymerization processes of butadiene, typically from about 7 to about 15 mole percent of the polybutadiene units exhibit the 1,2-addition configuration.

With respect to the B2 polybutadiene block, it is preferable that there is at least 25 mole percent vinyl in the B2 block. Preferably, the vinyl content in block B2 is from about 25 mole percent to about 80 mole percent of the condensed polybutadiene units, more preferably about 40 mole percent to about 75 mole percent of the units. polybutadiene have a 1,2-addition configuration, and even more preferably from about 50 to about 65 mole percent of the polybutadiene units have a 1,2-addition configuration.

The monovinyl aromatic hydrocarbon monomer content of the copolymer (preferably the styrene content) is from about 10% to about 40% by weight, based on the total weight of the block copolymer S-B1-B2 and optionally (S- B1-B2) nX. Preferably, the content of monovinyl aromatic hydrocarbon (advantageously styrene) of the block copolymers S-B1-B2, and optionally (S-B1-B2) nX, is from about 18% to about 35% by mass, more preferably d about 19% to about 32% by weight, based on the total weight of the copolymer.

In a preferred embodiment of the invention, the elastomer comprises a block copolymer of the formula S-B1-B2 alone.

In another preferred embodiment, S-B1-B2 is used in combination with a block copolymer of formula (S-B1-B2) nX in which each S is a monovinyl aromatic hydrocarbon block, preferably styrene, each B1 is a block of polybutadiene having a vinyl content of less than or equal to 15 mole percent, each B2 is a block of polybutadiene having a vinyl content of greater than or equal to 25 mole percent, n is an integer ranging from 2 at 6 and X is the residue of a coupling agent. When the block copolymers of formula (S-B1B2) nX are used, preferably, n is an integer ranging from 2 to 4, more preferably n = 2.

Advantageously, the block copolymers of the invention are in an essentially non-hydrogenated form. When the block copolymer composition comprises such a blend, the weight ratio of the S-B1-B2 / (S-B1B2) nX block copolymer is greater than or equal to about 1: 1. In a particularly preferred embodiment, the ratio is from about 1: 1 to about 10: 1 with the preferred ratio being from about 1: 1 to about 4: 1.

DUPLICATE

18634 ι

The mass average molecular weight of the elastomer is advantageously between 10,000 and 600,000 daltons, preferably between 30,000 and 400,000 daltons.

The block copolymers used in the invention are described in WO2008 / 137394. A process for their preparation is described in documents US Pat. No. 3,231,635; US-3,251,905; US-3,390,207; US-3,598,887; US-4,219,627; EP0413294; EP0387671; EP 0636654 and WO 94/22931.

The composition may include elastomers other than S-B1-B2 block terpolymers and (S-B1-B2) nX copolymers.

In particular, the composition according to the invention may contain other known elastomers for bitumen such as copolymers SB (block copolymer of styrene and butadiene), SBS (styrene-butadiene-styrene block copolymer), SIS (styreneisoprene-styrene). ), SBS * (styrene-butadiene-styrene star block copolymer), SBR (styrene-b-butadiene-rubber), EPDM (modified ethylene propylene diene), polychloroprene, polynorbornene, natural rubber, recycled rubber, polybutene, polyisobutylene , SEBS (copolymer of styrene, ethylene, butylene and styrene). Mention may also be made of the elastomers made from styrene monomers and from butadiene monomers allowing crosslinking without a crosslinking agent, as described in documents WO2007 / 058994 and by the applicant in patent application WO2011 / 013073. The teachings described in applications WO2007 / 058994 and WO2011 / 013073 are incorporated by reference in the present description, in particular the definitions of the polymers described in these two applications are incorporated by reference in the present description.

Advantageously, the S-B1-B2 block terpolymers and the (S-B125 B2) nX copolymers which have been defined above represent at least 50% by weight of the elastomers present in the composition, even more preferably at least 70% by weight. mass. According to a preferred variant of the invention, the elastomer consists essentially of S-B1-B2 block terpolymers and (S-BlB2) nX block copolymers.

The molecular mass of the copolymer is measured by GC chromatography with a polystyrene standard according to standard ASTM D5296-05.

The composition can also further comprise plastomers.

In particular, the composition according to the invention may also additionally contain one or more polymeric components chosen from the category of plastomers

DUPLICATES for known bitumen such as polyethylenes PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene vinyl acetate copolymer), EMA (polyethylene-methyl acrylate copolymer), copolymers of olefins and carboxylic esters unsaturated, EBA (polyethylene-butyl acrylate copolymer), copolymers of ethylene and esters of acrylic, methacrylic or maleic anhydride, ethylene-propylene copolymers, ABS (acrylonitrilebutadiene-styrene).

Advantageously, when the composition according to the invention comprises at least one plastomer as defined above, the block terpolymers S-B1-B2 and the copolymers (S-B1-B2) nX represent at least 50% by mass per relative to the total mass of all the terpolymers with blocks S-B1-B2, copolymers (S-B1B2) nX and plastomers present in the composition, even more preferably at least 70% by mass.

According to one variant of the invention, the composition may further comprise S-B1-B2 block terpolymers and (S-B1-B2) nX copolymers, at least one other elastomer as defined above and at least a plastomer as defined above.

Advantageously, when the composition according to the invention further comprises at least one other elastomer as defined above and at least one plastomer as defined above, the block terpolymers S-B1-B2 and the copolymers (S- B1-B2) nX 20 represent at least 50% by mass relative to the total mass of all the block terpolymers S-B1-B2, copolymers (S-B1-B2) nX, elastomers and plastomers present in the composition , even more preferably at least 70% by weight.

Other additives:

It is also possible to add to the bitumen / polymer composition of the invention, in a known manner:

a) adhesiveness dopes and / or surfactants. They are generally chosen from derivatives of alkylamines, derivatives of alkylpolyamines, derivatives of alkyl amidopolyamines and derivatives of quaternary ammonium salts, taken alone or as a mixture. The amount of tackifiers and / or surfactants in the bitumen / polymer composition is, for example, between 0.2% and 2% by weight, preferably between 0.5% and 1% by weight per weight. relative to the total mass of the bitumen / polymer composition.

b) waxes of animal, vegetable or hydrocarbon origin, in particular long-chain hydrocarbon waxes, for example polyethylene waxes or DUPLICATA waxes, optionally oxidized. Amide waxes such as ethylene bisstearamide can also be added.

c) paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C120). Paraffins are chosen from polyalkylenes. Preferably, the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins can be of petroleum origin or come from the chemical industry. Preferably, the paraffins are synthetic paraffins resulting from the conversion of biomass and / or natural gas.

These paraffins can also contain a large proportion of so-called "normal" paraffins, ie straight chain, unbranched linear paraffins (saturated hydrocarbons). Thus, paraffins can include 50 to 100% normal paraffins and 0 to 50% isoparaffins and / or branched paraffins. Preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins and / or branched paraffins. More preferably, the paraffins comprise from 50 to 100% normal paraffins and from 0 to 50% isoparaffins. Preferably, the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.

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

Preferably, the paraffins are FischerTropsch polymethylene paraffins sold by Sasol, in particular under the trademark Sasobit®.

d) fluxes 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.

(e) resins of plant origin such as rosins.

f) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides obtained from vegetable or animal oils.

g) detergent and / or anti-corrosion additives, in particular (but not limited to) chosen from the group consisting of amines, succinimides,

DUPLICATA alkenyisuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines; imidazolines.

h) lubricity additives or anti-wear agent, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- carboxylic acid derivatives. and polycyclic.

i) crystallization modifying additives, paraffin deposit inhibitor additives, pour point depressant additives; low temperature rheology modifiers such as ethylene / vinyl acetate (EVA) and / or ethylene / vinyl propionate (EVP) copolymers, ethylene / vinyl acetate / vinyl versatate (EA / AA / EOVA) terpolymers; ethylene / vinyl acetate / alkyl acrylate terpolymers; graft-modified EVA copolymers; polyacrylates; acrylate / vinyl acetate / maleic anhydride terpolymers; amidified maleic anhydride / alkyl (meth) acrylate copolymers which may be obtained by reaction of a maleic anhydride / alkyl (meth) acrylate copolymer and of an alkylamines or polyalkylamine having a hydrocarbon chain of 4 and 30 carbon atoms, preferably from 12 to 24 carbon atoms; amidified alpha-olefin / maleic anhydride copolymers which can be obtained by reaction of an alpha-olefin / maleic anhydride copolymer and an alkylamine or polyalkylamine, the alpha-olefin being able to be chosen from alpha-olefins C10-C50, preferably C16-C20 and the alkylamine or polyalkylamine having, advantageously, a hydrocarbon chain of 4 to 30 carbon atoms, preferably of 12 to 24 carbon atoms.

j) antioxidants, for example of hindered phenolic type or amine type of alkylated paraphenylene diamine type.

k) metal passivators.

1) acidity neutralizers.

m) additives making it possible to lower the mixing temperature of asphalts and mixes, those making it possible to improve the adhesion of bituminous binders to fillers and aggregates, such as for example polyisobutylene succinimides.

n) acids such as polyphosphoric acid or diacids, in particular fatty diacids.

The additives are used in amounts well known to those skilled in the art, depending on the nature of the additive, depending on the bitumen base and the expected properties.

When it comprises one or more additives, the bitumen base comprises from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from

DUPLICATE

IS

0.5% to 2.5% by mass of chemical additive relative to the total mass of the bitumen base.

The composition :

Advantageously, the bitumen / polymer composition comprises:

- bitumen,

- from 0.5% to 20% by mass of at least one elastomer as defined above,

- from 0.05% to 2.5% by mass of at least one olefinic polymeric adjuvant as defined above,

- from 0 to 5% of additives.

Even more advantageously, the bitumen / polymer composition comprises:

- bitumen,

- from 0.5% to 15% by mass of at least one elastomer as defined above,

- from 0.15 to 2% by mass of at least one olefinic polymeric adjuvant as defined above,

- from 0 to 5% of additives.

Advantageously, the bitumen / polymer composition essentially consists of:

- bitumen,

- from 0.5% to 20% by mass of at least one elastomer as defined above,

- from 0.05% to 2.5% by mass of at least one olefinic polymeric adjuvant as defined above,

- from 0 to 5% of additives.

Even more preferably, the bitumen / polymer composition consists essentially of:

- bitumen,

- from 0.5% to 15% by mass of at least one elastomer as defined above, - from 0.15 to 2% by mass of at least one olefinic polymer adjuvant as defined above,

- from 0 to 5% of additives.

The mass percentages are calculated relative to the total mass of said composition.

According to the invention, the elastomer / olefinic polymer adjuvant mass ratio is advantageously from 15/1 to 2/1, preferably from 12/1 to 5/2.

DUPLICATE

The manufacturing process:

The bitumen / polymer compositions of the invention can be prepared by any process known to those skilled in the art. Typically these methods include mixing the components and heating the mixture. Bitumen can be heated before mixing. Usually, the bitumen is heated before mixing, and the other components are added to the bitumen without having been previously heated.

According to a particular embodiment of the invention, a bitumen / polymer composition is prepared by bringing into contact:

- bitumen,

- from 0.5% to 20% by mass, preferably from 0.5% to 15% by mass of at least one elastomer,

- from 0.05% to 2.5% by mass, preferably from 0.15 to 2% by mass of at least one olefinic polymer adjuvant,

- possibly additives.

The mass percentages are calculated relative to the total mass of said composition.

The operation is carried out at temperatures ranging from 100 ° C to 200 ° C, preferably from 150 ° C to 200 ° C, more preferably from 160 ° C to 200 ° C, and with stirring for a period of at least 10 minutes, preferably from 1 hour to 24 hours, more preferably from 1 hour to 10 hours.

The method of the invention may be carried out by means of agitation producing high shear or agitation producing low shear. The method of the invention may comprise successive sequences with different agitation modes, for example the method of the invention may comprise at least two successive sequences of agitation, a first sequence producing agitation at high shear followed by a second sequence producing low shear agitation.

According to a preferred embodiment, the process for manufacturing the bitumen / crosslinked polymer composition comprises, for example, the following successive steps:

i) the bitumen, the heat-crosslinkable elastomer and the olefinic polymer adjuvant, optionally the additives, are introduced into a reactor, ii) the mixture is stirred until a homogeneous mixture is obtained and heated to a temperature ranging from 100 ° C. at 200 ° C, preferably from 150 ° C to 200 ° C, more preferably from 160 ° C to 200 ° C, for a period of at least 10 minutes, preferably 1 hour to 24 hours, more preferably 1 hour to 10 o'clock.

DUPLICATE

In the implementation described above, the olefinic polymer admixture can be incorporated into the bitumen before or after the heat-crosslinkable elastomer, simultaneous incorporation also being possible.

The order of introduction of the different constituents does not have a significant influence on the mechanical properties of the bitumen / polymer composition thus obtained.

In particular, the olefinic polymer adjuvant is incorporated into the bitumen before or after the elastomer.

Also particularly, the olefinic polymer builder and the elastomer are incorporated into the bitumen.

According to another preferred embodiment, the process for manufacturing the bitumen / crosslinked polymer composition comprises, for example, the following successive steps:

i) the bitumen, the heat-crosslinkable elastomer and the olefinic polymer additive, optionally the additives, are introduced into a reactor, ii) the mixture is stirred at a temperature ranging from 100 ° C to 200 ° C, preferably 150 ° C to 200 ° C, more preferably from 160 ° C to 200 ° C, for a period of at least 1 minute, preferably between 1 min and 2 hours, more preferably between 1 min and 30 min, then homogenized by passage through a high shear mill, iii) the mixture obtained in step ii) is then transferred to a maturation tank for a period of at least 30 min, preferably from 30 min to 24 hours, more preferably from 1 hour to 10 hours before storage or use.

Preferably, the stirring at high shear, and in particular the stirring carried out by passing through a high shear mill, makes it possible to facilitate the good dispersion and the good distribution of the polymer and of the olefinic polymer adjuvant.

Implementation of bitumen / polymer compositions according to the invention:

Various uses of the bitumen / polymer compositions obtained according to the invention are envisaged. In particular, the bitumen / polymer compositions can be used for the preparation of a bitumen / polymer binder. The bitumen / polymer binder according to the invention can be used in combination with aggregates, in particular road.

With regard to road applications, the invention relates in particular to bituminous mixes as materials for the construction and maintenance of pavement bodies and their coating, as well as for carrying out all road works.

By bituminous mix is meant a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers.

DUPLICATE

The bituminous mix comprises a bitumen / polymer binder according to the invention, and optionally mineral and / or synthetic fillers, preferably chosen from fines, sand, chippings and recycling mills. The aggregates are mineral and / or synthetic aggregates, in particular, recycling mills, with dimensions greater than 2 mm, preferably between 2 mm and 20 mm.

The bitumen / polymer binder according to the invention can advantageously be used to prepare a surface coating, a hot mix, a warm mix, a cold mix, a cold mix or a severe emulsion.

With regard to road applications, the invention also relates to asphalts 10 as materials for making and covering sidewalks.

By asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers.

An asphalt comprises a bitumen / polymer binder according to the invention and mineral fillers such as fines, sand or chippings and / or synthetic fillers. Mineral fillers consist of fine (particles with dimensions less than 0.063 mm), sand (particles with dimensions between 0.063 mm and 2 mm) and possibly chippings (particles with dimensions greater than 2 mm, preferably between 2 mm and 4 mm).

Asphalts have 100% compactness and are mainly used to make and cover sidewalks, while asphalt has a compactness of less than 100% and are used to make roads. Unlike asphalt, asphalts are not compacted with a roller during their placement.

Another aspect of the invention is the use of a bitumen / polymer composition in various industrial applications, in particular to prepare a waterproofing coating, a membrane or an impregnation layer.

As regards the industrial applications of the bituminous compositions according to the invention, mention may be made of the manufacture of waterproofing membranes, anti-noise membranes, insulation membranes, surface coatings, slabs of ¹ .

I carpet, layers of impregnation.

A subject of the invention is also the use of bitumen / polymer binders, of mixes and of mastic asphalt according to the invention for the manufacture of road surfaces, pavements, sidewalks, roads, urban developments. , floors, waterproofing of buildings or structures, in particular for the manufacture in road application, of foundation layers, base layers, base layers, i 35 surface layers such as layers of bonding and / or wearing courses.

Experimental part :

A- Materials and methods î DUPLICATE i

I I

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

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

- Ball and ring softening temperature (TBA): unit = ° C, standard 5 EN 1427.

- Elastic return at 25 ° C (R25): unit =%, standard EN 13398.

- Tensile test at 5 ° C, 100mm / min (ε max represents the maximum elongation at break): unit =%, standard EN 13587.

- Stability: the storage stability is evaluated by measuring the difference in penetrability and the difference in TBA after 3 days of storage at 180 ° C.

Raw materials :

- Bitumen base (B): a 35/50 grade bitumen base having a P25 penetrability of 37 1/10 mm and a TBA of 52.6 ° C and available commercially from the TOTAL group under the brand AZALT® was used.

- Bitumen base (B1): a 35/50 grade bitumen base having a P25 penetrability of 39 1/10 mm and a TBA of 53.0 ° C and available commercially from the TOTAL group under the brand AZALT® was used.

- Bitumen base (B2): a 70/100 grade bitumen base having a P25 penetrability of 75 1/10 mm and a TBA of 45.4 ° C and commercially available from the TOTAL group under the brand AZALT® was used. .

- Bitumen base (B3): a grade 10/20 bitumen base having a P25 penetrability of 14 1/10 mm and a TBA of 66.6 ° C and available commercially from the TOTAL group under the MODULOTAL® brand was used.

- Bitumen base (B4): a 70/100 grade bitumen base having a P25 penetrability of 77 1/10 mm and a TBA of 46 ° C and commercially available from the TOTAL group under the brand AZALT® was used.

- Bitumen base (B5): a 35/50 grade bitumen base having a P25 penetrability of 37 1/10 mm and a TBA of 53.2 ° C and available commercially from the TOTAL group under the brand AZALT® was used.

- Bitumen base (B6): a grade 50/70 bitumen base having a P25 penetrability of 55 1/10 mm and a TBA of 49.6 ° C and available commercially from the TOTAL group under the brand AZALT® was used.

- Bitumen base (B7): a 160/220 grade bitumen base having a P25 penetrability of 176 1/10 mm and a TBA of 39.0 ° C and commercially available from the TOTAL group under the brand AZALT® was used. .

- Polymer adjuvant (Adj): ethylene / butyl acrylate / glycidyl methacrylate terpolymer in proportions by mass, respectively of

DUPLICATE

70/21/9 and having a melt index MFR (English acronym for “Melt Flow Rate”) (190 ° C / 2.16 kg) of 8g / 10min, calculated according to standard ASTM D1238-ISO1133. This polymer is commercially available under the name Elvaloy® 4170 from the company Dupont.

- Elastomer (E): a mixture based on SB1-B2 block terpolymer was used, also comprising copolymer (S-B1-B2) nX with S representing a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25 000, B1 is a polybutadiene block having a vinyl content less than or equal to 15 mole percent, B2 is a polybutadiene block having a vinyl content greater than or equal to 25 mole percent, the ratio of B1 / B2 is greater than or equal to 1: 1, the S-B1-B2 block copolymer has a peak molecular weight of 40,000-200,000, n is an integer ranging from 2 to 6, X is the residue of a coupling, the (S-B1-B2) nX block copolymer has a peak molecular weight which is 1.5 to 6.0 times the peak molecular weight of the S-B1-B2 block copolymer, wherein the mass ratio S15 B1-B2 / (S-B1-B2) nX is greater than or equal to 1: 1. The vinyl group content of the mixture is 20.2% by mass relative to the total mass of the polymer mixture. es. The weight average molecular mass of the mixture is 235,000 Daltons. This elastomer is available from the company Kraton.

- Elastomer (E1): a styrene / butadiene / styrene (SBS) block copolymer containing 30.5% by weight of styrene and 69.5% by weight of butadiene was used. The content of 1,2-vinyl group is 27.8% by weight relative to the total weight of copolymer. The copolymer has a molecular weight (Mw) of 142,500 Daltons and a polydispersity index I _p of 1.09. This copolymer is commercially available from the company KRATON under the name DI 192.

B- Preparation of bitumen / polymer compositions:

Compositions C1 to C5, Cl3 and C14 were prepared corresponding to the mixtures detailed below in Tables 1 and 1a with the reaction time indicated.

The process comprises the following steps:

• Mixing of components at 180 ° C.

· Introduction of the components into a Silverson ® reactor and stirring for minutes to obtain a homogeneous mixture.

• Then the mixture is stirred for 6 hours: at 400 revolutions / min at 180 ° C.

Composition C9 corresponding to the mixture detailed below in Table 1 bis was prepared with the reaction time indicated.

The process comprises the following steps:

• Mixing of components at 180 ° C.

DUPLICATE • Introduction of the components into a Silverson ® reactor and stirring for 3 hours to obtain a homogeneous mixture.

• Then the mixture is stirred for 2 hours: at 400 rev / min at 180 ° C

Compositions C6 to C8 and C10 to C12 were prepared corresponding to the mixtures detailed below in Tables 1 and 1 bis with the reaction time indicated.

The process comprises the following steps:

• Mixing of components at 180 ° C.

• Introduction of the components into a Silverson ® reactor and stirring for 10 3 hours to obtain a homogeneous mixture at 180 ° C, • the mixture is then stirred for 2 hours at 400 rev / min and at 180 ° C, • the mixture thus obtained is diluted with a bitumen base previously brought to a temperature of 180 ° C., then the mixture is subjected to stirring at 400 revolutions / min at 180 ° C. for 1 hour.

The amounts indicated in the tables are percentages by mass relative to the total mass of the composition. Compositions C1, C2, Cl3 and C14 are comparative, compositions C3 to Cl2 are according to the invention.

Composition Cl C2 C3 C4 C5 C6 C7 B 97.5 96.5 97.25 96 - - - Bl - - - - 96.72 - - B2 - - - - - 57.15 - B3 - - - - - 40 40 B4 - - - - - 56.62 B5 - - - - - - - B6 - - - - - - - B7 - - - - - - - E 2.5 3.5 2.5 3 2.85 2.58 2.94 El - - - - - - - Adj - - 0.25 1 0.43 0.27 0.44 Reaction time 6h 6h 6h 6h 6h 6h 6h

Table 1: Prepared compositions C1 to C7

DUPLICATE

Composition C8 C9 CIO Eyelash C12 C13 C14 B - - - - - - Bl - - - - 96.72 96.55 B2 - - - - - - - B3 - - - - - - - B4 - 94.3 51.87 - 34 - - B5 97.15 - - 96.48 - - - B6 - - 45 - - - - B7 - - - - 62.83 - - E 2.58 5 2.75 3 2.77 - - El - - - - - 2.85 3.2 Adj 0.27 0.7 0.38 0.52 0.4 0.43 0.43 Reaction time 6h 5h 6h 6h 6h 6h 6h

Table Ibis: compositions prepared C8 to C14

C- Industrial process for manufacturing bitumen / polymer composition according to the invention at high shear and in a continuous line:

A bitumen / polymer composition Cl5 was prepared by means of an industrial process at high shear and in continuous line by mixing at a temperature between 185 and 195 ° C and at high shear:

DUPLICATE

- 97.07% of a 35/50 grade bitumen base having a P25 penetrability of 42 I / IO mm and a TBA of 52 ° C (commercially available from the TOTAL group under the brand AZALT®),

- 2.57% of polymer E and

- 0.36% of Adj; the percentages being given by weight by mass relative to the total weight of the composition.

The mixture thus obtained is then mixed for 4 hours at a temperature between 185 and 195 ° C.

IO D- Industrial process for manufacturing bitumen / polymer composition according to the invention by grinding with external recirculation:

A bitumen / polymer Cl6 composition was prepared by means of an industrial process by grinding with external recirculation by mixing for 3 hours at a temperature of 195 ° C:

- 96.72% by weight of a grade 30/45 bitumen base having a P25 penetrability of 36 l / ΊΟ mm and a TBA of 54.6 ° C (commercially available from the TOTAL group under the brand AZALT®),

- 2.85% by weight of polymer E and

- 0.43% by weight of Adj; the percentages being given by weight by mass relative to the total weight of the composition.

The mixture thus obtained is then mixed for 2 hours at a temperature of 195 ° C.

E- Results:

The compositions are tested according to the methods explained above. The results are reported in Table 2:

Composition Cl C2 C3 C4 C5 C6 C7 C8 Penetrability (dmm) 31 32 33 31 34 33 32 33 TBA (° C) 57.6 63.8 58.4 62.6 60.4 60 62.2 57.8 Springback (%) 66 86 71 77 74 70 76 67 Traction Energy at 5 ° C 400% (J / cm ² ) - - 17.51 18.46 21.9 19.4 22.1 21.7 Elongation Max (%) 59 305 700 700 688 700 687 700 Stability Δ 3 12 1 3 1 0 0 0

DUPLICATE

storage 3d to 18O ° C Penetrability (dmm) Δ TBA (° C) 0.2 21.8 0.8 3.4 l 0.6 0.2 0

Table 2: properties of the prepared compositions C1 to C8 ND: not determined

Composition C9 CIO Eyelash C12 C13 C14 C15 C16 Penetrability (dmm) 48 53 30 95 33 34 37 33 TBA (° C) 89.5 61.2 62.4 49.8 59.2 60.8 60 64 Springback (%) 95 ND 76 69 62.8 75 76 78 Traction at 5 ° C Energy at 400% (J / cm ² ) 15.25 14.08 22.4 6 6.52 22.51 22.4 8 22.1 5 19.8 Max Elongation (%) 700 700 700 700 295 457 682 695 Storage stability 3 days at 180 ° C Δ Penetrab ility (dmm) 1 0 0 1 2 1 1 0 Δ TBA (° C) 0.5 0.2 0.8 0.2 0 0.8 0.8 0.4

Table 2a: properties of the compositions prepared C9 to C16 ND: not determined

DUPLICATE

A synergistic effect is observed between the block polymer according to the invention and the olefinic polymer adjuvant, which makes it possible to obtain a very significant improvement in the mechanical properties, in particular the elastic properties, in particular tensile properties at 5 ° C., with quantities very low block polymer system / adjuvant.

This synergistic effect between the block polymer and the olefinic polymer additive also makes it possible to obtain a significant improvement in the hot storage stability, in particular storage stability at 180 ° C., of the bitumen / polymer composition with very high amounts. low polymer block / adjuvant system.

In addition, it is observed that there is no synergistic effect between the block polymer El and the olefinic polymer adjuvant because the tensile properties at 5 ° C, with very small amounts of block polymer system / adjuvant are less than 500%.

Consequently, it is demonstrated that the combination of the block polymer and of the olefinic polymer adjuvant according to the invention makes it possible to obtain a very significant improvement in the mechanical properties, in particular of the elastic properties, in particular of traction at 5 ° C., with very small amounts of block polymer system / adjuvant.

F- Preparation of bituminous mixes and measurement of their mechanical properties:

A bituminous mix (EB1) is respectively obtained from composition Cl6 according to the invention and from aggregates having the granular cut described in Table 3:

Cut (mm) 0/2 2/4 4/6 6/10 Filler Weight (%) 39 10 12 38 1

Table 3: Particle size composition

The bituminous mix (EB1) is prepared as follows:

- The aggregates are brought to a temperature of 175 ° C for a period of approximately 8 hours 30 minutes,

- The bituminous composition C16 is heated to 175 ° C and then poured onto the previously heated aggregates, the mixture thus obtained is kneaded for approximately 90 seconds at 175 ° C.

The bituminous mix thus obtained has a 35 C16 bituminous composition content of 5.7% by mass relative to the total mass of the mix.

DUPLICATE

A bituminous mix is characterized as a high modulus asphalt concrete for wearing course or binding type EB 10, also called class 3 BBME according to standard NF EN 13108-1, if it has at least the following characteristics described in the table 4:

Asphalt EB 1 BBME class 3 specifications, according to standard EN 13108-1 Duriez test at 18 ° C ⁽¹⁾ (r / R) 0.89 > 0.8 30,000 cycle rutting test 1.7 <5 Complex modulus test at 15 ° C and at 10Hz (MPa) ⁽³⁾ 11,500 > 11,000 Fatigue test (pdef for 10 ⁶ cycles) ⁽⁴⁾ 199 > 100

Table 4: Mechanical properties of the bituminous mix (EBl) ^(l) Test of resistance to stripping in water according to standard EN 12697-12, reflecting the adhesion between the bitumen / polymer composition and the aggregates.

⁽²⁾ Rutting resistance test according to standard EN 12697-22, reflecting the capacity of the asphalt mix to resist creep linked to the application of traffic.

⁽³⁾ Measurement of the complex modulus of rigidity according to standard NF EN 12697-26, reflecting the capacity of the asphalt mix to withstand stresses.

⁽⁴⁾ 2-point flexural fatigue strength test according to standard EN 12697-24, 15 reflecting the capacity of the asphalt mix to maintain intact the properties of the asphalt mix depending on the repetition of the application of charges.

The EB1 bituminous mix obtained from composition C16 according to the invention exhibits mechanical properties fulfilling the conditions of use of this mix as class 3 BBME for the manufacture of wearing courses or binding layers subjected to heavy loads. traffic solicitations

DUPLICATE

Claims (13)

l. Bitumen / polymer composition comprising: - bitumen, 5 - at least one elastomer, and - at least one olefinic polymer adjuvant functionalized with at least glycidyl functional groups, characterized in that: • the elastomer is chosen from heat-crosslinkable block copolymers of formula S-B1-B 2, wherein S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, B1 is a polybutadiene block having a vinyl content of 15 mole percent or less, B2 is a polybutadiene block having vinyl content greater than or equal to 25 mole percent, the BI / B2 mass ratio is greater than or equal to 1: 1, and wherein the SB 1 -B2 block copolymer has a peak molecular weight of 40 000 to 200,000; • the elastomer can also comprise at least one block copolymer: heat-crosslinkable corresponding to the formula (S-B1-B2) nX in which each S j represents a monovinyl aromatic hydrocarbon block having a molecular weight of! peak of 10,000 to 25,000, each B l represents a polybutadiene block having a 20 mole percent or less, each B2 represents a polybutadiene block having a vinyl content of 25 mole percent or more, n is an integer ranging from 2 to 6, and X is the residue of a coupling agent, wherein the B1 / B2 mass ratio is greater than or equal to 1: 1, and the block copolymer (S-B1-B2) nX has a peak molecular weight which is 1.5 to 6.0 times the peak molecular weight of the S-B1-B2 block copolymer; and the elastomer / adjuvant mass ratio in the composition ranges from 15/1 to 2 / l. ¹ 2. The composition of claim 1, wherein the mass ratio: S-B1-B2 / (S-Bl-B2) nX 30 is greater than or equal to 1: 1, preferably 1: 1 to 10: 1, and more preferably 1: 1 to 4: 1. I 3. A composition according to claim 1 or claim 2, wherein S represents styrene. । 35 DUPLICATE 3l 4. Composition according to any one of the preceding claims, which comprises from 0.5% to 20% by mass of elastomer relative to the total mass of the composition, preferably from 0.5 to 15%. 5. Composition according to any one of the preceding claims, which comprises from 0.05% to 2.5% by mass of olefinic polymer builder relative to the total mass of the composition, preferably from 0.15 to 2. %. 6. A composition according to any preceding claim, wherein the olefinic polymer builder is selected from the group consisting of: (a) copolymers, random or block, of ethylene and of a monomer selected from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99, 7% by mass of ethylene; (b) the terpolymers, random or block, of ethylene, of a monomer A 15 chosen from vinyl acetate and alkyl acrylates or methacrylates in Ci to Ce and of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and from 0.5% to 15% by weight mass of units derived from monomer B, the remainder being formed from units derived from ethylene; and (C) the copolymers resulting from the grafting of a monomer B chosen from glycidyl acrylate and glycidyl methacrylate, on a substrate consisting of a polymer chosen from polyethylenes, polypropylenes, random or block copolymers of ethylene and vinyl acetate and random or block copolymers of ethylene and C 1 to C 6 alkyl acrylate or methacrylate comprising from 40% to 99.7% by weight of ethylene, said graft copolymers comprising from 0.5% to 15% by weight of graft units derived from the monomer B, (d) mixtures of at least two compounds (a), (b) and (c). 7. The composition of claim 6, wherein the olefinic polymer adjuvant is selected from random or block terpolymers of ethylene, of a monomer A selected from vinyl acetate and C alkyl acrylates or methacrylates. । to Cé and of a monomer B chosen from glycidyl acrylate and DUPLICATA glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% in mass of units derived from monomer B, the remainder being formed from units derived from ethylene. 5 8. Composition according to claim 7, in which the olefinic polymer adjuvant is chosen from random terpolymers of ethylene, of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a B monomer chosen. from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and, from 0.5% to 15% by weight of 10 units derived from monomer B, the remainder being formed from units derived from ethylene. 9. A process for preparing a bitumen / polymer composition according to any one of claims 1 to 8, characterized in that it is brought into contact, operating at temperatures between 100 ° C and 200 ° C and with stirring. for a period of at least 10 minutes: - bitumen, - from 0.5% to 20% by mass of at least one elastomer, - from 0.05% to 2.5% by mass of at least one olefinic polymeric adjuvant, - optionally additives. 10. Asphalt characterized in that it comprises at least one bitumen / polymer composition according to any one of claims 1 to 8, and mineral and / or synthetic fillers. 25 11. Bituminous mix characterized in that it comprises at least one bitumen / polymer composition according to any one of claims 1 to 8, aggregates, and optionally mineral and / or synthetic fillers. 12. Use of at least one bitumen / polymer composition according to any one of claims 1 to 8 for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold mix, a cold mix, serious emulsion, said binder being associated with aggregates and / or recycling mills. DUPLICATE 13. Use of at least one bitumen / polymer composition according to any one of claims 1 to 8, for preparing a waterproofing coating, a membrane or an impregnation layer.