EP2462196A2

EP2462196A2 - Supramolecular polymer-containing bituminous composition

Info

Publication number: EP2462196A2
Application number: EP10752895A
Authority: EP
Inventors: Juan Antonio Gonzalez Leon; Jean-Philippe Gillet; Gilles Barreto; Manuel Hidalgo; Vincent Luca
Original assignee: Carbonisation et Charbons Actifs CECA SA
Current assignee: Carbonisation et Charbons Actifs CECA SA
Priority date: 2009-08-04
Filing date: 2010-07-29
Publication date: 2012-06-13
Also published as: FR2948944A1; US8252865B2; US20120046395A1; FR2948944B1; WO2011015773A3; US8076398B2; WO2011015773A2; US20110034593A1

Abstract

The present invention relates to a bituminous composition containing at least one bitumen and at least one condensation polymer capable of forming a supramolecular structure and including one or more associative groupings. The present invention also relates to the use of such a bituminous composition in the production of coated materials usable for coating surfaces suitable for motor vehicles, in the production of damp-proofing coatings, and in the production of adhesive compositions.

Description

Bituminous composition containing a supramolecular polymer

Field of the invention

The present invention relates to bituminous compositions comprising specific polymeric materials, used in particular in the preparation of asphalt with improved mechanical properties. In particular, the present invention relates to bitumen compositions containing polymers capable of forming a supramolecular structure imparting improved mechanical properties to asphalt, and their applications. Examples of such applications include roofing, the manufacture of mixes containing mineral aggregates for the construction or maintenance of sidewalks, roads, highways, car parks or runways and service roads of airports, and any other vehicular surface.

Bitumen or asphalt is the heaviest portion recovered during the petroleum distillation process. Because of the origins and processes of various distillations of such oils, the resulting bitumen can have a wide range of properties and characteristics. In the present invention, the term bitumen refers not only to the product obtained from petroleum by direct distillation or by reduced pressure distillation of petroleum, but also the product obtained by extracting pitch and oil sands, the product of the oxidation and / or fluxing with carbonaceous solvents, including paraffins and waxes of such bituminous materials, as well as blown and semi-blown bitumens, synthetic bitumens such as those described in FR 2 853 647 A1, pitches , petroleum resins or indene-coumarone resins mixed with aromatic and / or paraffinic hydrocarbons, their mixtures and mixtures of such bituminous materials with acids, etc.

The main application of bitumen is the inclusion in asphalt where the bitumen is mixed with mineral aggregates which can be of various sizes, shapes and chemical natures. These mixes are particularly used in the construction or maintenance of sidewalks, roads, highways, car parks or runways and service roads of airports, and any other road surface. In the present invention, mineral aggregates are obtained from quarries or recovered in older mixes (as described in AFNOR XP P98-135, December 2001, as well as in the Asphalt Handbook MS-4 T edition, published by the Asphalt Institute), or from the demolition of buildings, or are mixtures of these products. Other common components of the mix include organic and inorganic fibers, eg glass, metal or carbon, as well as cellulose, cotton, polypropylene, polyester, vinyl and polyamide fibers. It is known to those skilled in the art that polymers can be added to the bitumen to produce mixes whose mechanical properties are improved. Polymers are large molecules formed by the chemical bonding of several repeating units or monomers. Modification of the bitumen by high molecular weight polymers (greater than about 10,000 g / mol) is generally necessary to improve the mechanical behavior of a bituminous mix.

Although there are solutions for hardening the bitumen, for example the incorporation of paraffins or polyphosphoric acid, in order to increase the stiffness of the bitumen at high temperatures to avoid rutting these solutions can only be partial because the modified bitumen retains a high thermal sensitivity (unlike polymer-modified bitumens, where it is improved at high and low temperatures), which creates or even amplifies problems at low temperatures, for example lack of flexibility.

The modification of the bitumen by the polymers is therefore very often used to increase its flexibility at low temperature, that is to say below room temperature and up to about -40 ⁰ C, and this same modification by polymers increases the softening point of the bitumen. It can also increase the cohesion and rigidity of the bitumen at high use temperatures, and thus those of an asphalt mix made from this bitumen, which improves its resistance to rutting. Examples of polymers commonly used in bitumen modification include: styrene-butadiene rubbers, styrene / butadiene block copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylate copolymers, polyethylene and other alpha-polyolefins (see "Asphalt binder testing manual", Asphalt Institute 2007). The use of non-crosslinked low molecular weight polymers, also known as oligomers, or other small molecules, can not alter bitumen as dramatically as polymers.

[0007] GB 1156793 describes the use of polyamides in the modification of bitumen for surface coating compositions. The authors claim that the addition of the polyamide resin gives the bitumen the rheological property called thixotropy, which bitumen does not inherently possess.

The incorporation of polymers into the bitumen, even at low levels commonly used (between 2% and 6% of polymer), is not an easy operation. Polymers and bitumen have at best partial compatibility, which generally forces the polymer to undergo phase separation from the bitumen over time. In addition, because of the high viscosities of the molten polymers, the mixing process requires high temperatures and long times with vigorous stirring to achieve good dispersion of the polymer in the bitumen. The temperatures necessary to obtain the dispersion of the polymer in the bitumen are generally higher than the storage and manufacturing temperatures determined by the nature of the pure bitumen.

For example, US Pat. No. 5,618,862 mentions the dispersion of a styrene / butadiene copolymer with a molecular weight of 100,000 daltons at 3.5% in bitumen with a penetration of 80/100, which requires 2.5 hours for 175 ⁰ C to be homogeneous. For this type of bitumen, the typical storage temperature of pure bitumen is between 140 ^° C. and 160 ^° C. The higher temperatures required for the dispersion of the polymer in the bitumen may also be unfavorable for the properties of the bitumen, because they accelerate its oxidation. The addition of a crosslinking agent, for example a sulfur compound, is a solution commonly used in polymer-modified bitumens to further increase their performance. Such a network makes it possible to further increase the viscosity of the bitumen and avoids the phenomenon of phase separation. In addition, such sulfur compounds, combined with the high temperatures necessary to achieve the mixture, pose significant safety problems during the manufacturing process of the modified bitumen.

Because of the difficulty of developing a polymer-modified bitumen, the process is accessible only to asphalt refiners or large construction companies, the only ones able to invest in such large proportions in the appropriate mixing equipment.

The use of a modified bitumen to manufacture a mix usually results in the modification of the manufacturing process compared to the unmodified bitumen. In the case of emulsions, for example, the addition of polymers may restrict the qualities of the bitumen used, because the process of emulsification with water limits the temperature at which the bitumen can be added to avoid the boiling of water. asphalt emulsion, which is unfavorable to its stability. The higher temperature viscous bitumen grades can be used to make emulsions in water at superatmospheric pressures to prevent boiling of water. However, this adds a certain complexity to the process for manufacturing the emulsion. In the case of the manufacture of hot mixes, it is necessary to apply the higher temperatures for manufacturing, laying and compaction in case of use of modified bitumen. The higher viscosity of polymer-modified bitumen over pure bitumen can also lead to difficulties in processing methods at temperatures below 100 ^° C and above room temperature, which reduces the overall fluidity of the bitumen.

This can be interesting in practice when the addition of a polymer material to the bitumen can be carried out without significant increase in its manufacturing temperature. compared to pure bitumen, while obtaining a significant improvement in the mechanical properties of the resulting mix.

In addition, a reduction in temperature during the dispersion of the polymer and the method of manufacturing the asphalt would be interesting in practice, because it would provide several advantages. Reducing the temperature of the dispersion and / or its duration reduces the proportion of oxidation and aging of bitumen, which increases the service life of the final application, for example in the case of a bituminous mix. road. If such a reduction in temperature can be transposed to the process of manufacture of the mix, it will reduce the amount of energy consumed during the dispersion and, more importantly, during the manufacturing process of the mix. Lowering aggregate and bitumen temperatures during the asphalt manufacturing process would also significantly reduce the amount of pollutant emissions, including CO ₂ and other greenhouse gases.

There are several approaches to reduce the time and temperature required for the dispersion of polymers in the bitumen. One of these approaches is the addition of a solvent during mixing, which can also be used to disperse the polymer before adding the bitumen. The use of volatile solvents is not a practical option because of their polluting effect and the difficulty of using them at high temperatures. Other solvents may be employed, for example vegetable oils or their derivatives. The use of such solvents in the production of bitumen-modified asphalt often results in the softening of the material and an increase in rutting.

[0015] WO 2005/087869 discloses a polymer modified bitumen composition which includes the use of a vegetable oil monoalkyl ester as a solvent to facilitate mixing. In addition, an amide additive is also added to partially offset the loss of mechanical properties following the addition of the alkyl ester. The addition of about 6% of rapeseed oil methyl ester to dissolve the polymer beforehand, as described in one of the examples, nevertheless softens the mix. In addition, a temperature greater than 160 ^° C. and 30 minutes of stirring remain necessary for the incorporation of the polymer solution with penetration bitumen 160/220. The typical storage temperature of this type of pure bitumen is between 130 ^° C. and 150 ° C.

[0016] US 6,156,113 describes another approach to improving the mechanical properties of the final bitumen composition, while maintaining low viscosities at the manufacturing temperatures. In this patent, mono-esters of fatty acids are added to the bitumen to reduce the viscosity by solvation effect under the manufacturing conditions, while the crosslinking of these esters is obtained by adding a metal catalyst under the conditions of the application. This process can last several days. Although this method allows for low viscosities in the manufacturing conditions and an improvement in mechanical properties of the final mix, the use of certain metal catalysts can be limited because of their negative impact on the environment and the human being.

[0017] FR 2 871 804 proposes the use of a polymer-bitumen mixture containing a high polymer content, called a masterbatch. This mixture is prepared using an extrusion device and then diluted with bitumen to quickly obtain the correct polymer content. The defect of this solution is that a specific device remains necessary to mix the polymer and the bitumen in order to obtain the masterbatch, which entails a considerable economic investment.

[0018] FR 2 924 121 describes the use, in bitumen compositions, of organogel molecules that improve the mechanical properties of bitumen by forming thermoreversible networks, with a reduced viscosity at application temperatures. However, the process for adding the organogel molecules requires a relatively high temperature (170 ^° C. for a pure initial penetration bitumen 50), and a relatively long mixing time of 2 hours.

The main problem of the addition of normal or conventional polymers in the bitumen being their high viscosity, one of the solutions would be that the polymer has good mechanical properties at application temperatures of the mix (between about -20 ^{° C).} C and 70 ° C) and a very low viscosity at elevated temperatures (above 100 ^° C.). A low viscosity at high temperature would indeed greatly facilitate the dispersion of such polymer in the bitumen at lower temperatures, under milder mixing conditions and with shorter mixing times. This would also facilitate the use of the modified bitumen due to the lower temperatures and the shorter process time.

Polymeric materials having such properties can be obtained by using small or medium sized molecules behaving as monomers (or oligomers) and assembling into a supramolecular polymer structure through bonds. not covalent at low temperature, the structure dissociating at high temperature.

[0021] WO 2001/07396 discloses a polymer-type material obtained from oligomers which can be associated in large structures by hydrogen bonds between specific carboxylic acid and alcohol functional groups. The resulting material has mechanical properties far superior to those of the original monomer, these properties improving as the number of associated functional oligomers increases. No application to bitumen is discussed in this invention.

[0022] WO 2003/059964 discloses another supramolecular polymer, based on a different chemistry. In this case, properties similar to those of a polymer are also obtained by interconnecting smaller molecules by hydrogen bonds. No application to bitumen is discussed in this invention.

[0023] WO 2006/087475 discloses an elastomeric material formed by the supramolecular assembly of smaller molecules. The rubbery material according to this invention becomes liquid above a certain temperature due to the dissociation of the hydrogen bonds. The transition between elastic polymer and liquid depends on the temperature and is reversible. No application to bitumen is discussed in this invention.

In a first aspect, the present invention relates to a bituminous composition, said bituminous composition being in the form of a dispersion or a solution, of similar mechanical properties to those obtained with bitumens modified with conventional polymers in the final application conditions, and comprising a bitumen and a polycondensate. The bituminous composition according to the present invention comprises at least one polycondensate capable of forming a supramolecular structure. This means that said polycondensate, as an isolated object, comprises at least one associative group capable of forming inter and / or intramolecular physical bonds to construct a physical network, resulting in a low viscosity polymer at elevated temperature (at these temperatures). , the network tends to dissociate) and a high modulus at low temperature (at these temperatures, the network is mainly in associated form).

Surprisingly, the bituminous composition according to the invention has improved mechanical properties compared to those of bitumen and therefore for its final application, which can be among other things the road surface coating, the waterproofing of surfaces, the preparation of adhesives, for example asphalt for roads, car parks or airport runways, bonding layers, surface mixes, surface treatment, surface impregnation, roof covering or roofing membranes, wall and floor coverings, and generally waterproofing, as well as bituminous adhesive compositions.

The present invention has the advantage that the process of adding the polycondensate bitumen is simple way to temperatures similar to those to which the pure bitumen is stored. Incorporation of such a polycondensate into the bitumen is considerably simpler than in conventional polymer modified bitumens because of its low viscosity at elevated temperature. Its dispersion in the bitumen requires significantly lower temperatures and significantly shorter mixing times under moderate to low shear conditions, compared to a conventional polymer modified bitumen. The present invention does not require any other chemical compound, such as a catalyst or crosslinking agents, for obtain improved mechanical properties under the conditions of application, although it is possible to add, as well as other conventional additives, if appropriate.

One of the other advantages of the invention over other bituminous compositions comprising molecules having similar associative groups, capable of forming a thermoreversible network, is the improved resistance to moisture of the resulting mix.

The bituminous composition according to the present invention is in the form of a dispersion or a solution, and comprises at least one bitumen and at least one polycondensate comprising one or more associative groups capable of forming a supramolecular structure.

The term "bitumen" refers to a bituminous material obtained by distillation of petroleum under atmospheric or reduced pressure, the product resulting from the extraction of pitch and oil sands, the product of oxidation and / or fluxing with carbonaceous solvents, including paraffins and waxes of such bituminous materials as well as blown or semi-blown bitumens, synthetic bitumens (such as those described in FR 2 853 647), pitches, petroleum resins or indene-coumarone resins mixed with aromatic and / or paraffinic hydrocarbons, mixtures thereof and mixtures of such bituminous materials with acids, etc.

In the present invention, the polycondensate (s) comprising one or more associative groups capable of forming a supramolecular structure may be any type of polymer obtained by a polycondensation reaction, and comprising at least one, preferably at least two, and most preferably at least three associative groups capable of forming a supramolecular structure.

The polycondensation reaction may be a reaction between a carboxylic acid function and an amine function (in this case, the polycondensate is a polyamide), or between a carboxylic acid function and an alcohol function (in this case, the polycondensate is a polyester), or between an isocyanate function and an alcohol or amine function (in this case, the polycondensate and a polyurethane or a polyurea).

More specifically, said polycondensate, mixed with at least one bitumen to form the bituminous composition according to the present invention, comprises: α) at least two repeating units of formula (A1):

where X represents an oxygen atom, a group -C (R ¹ ) (R ² ) -, or a group -N (R ¹ ) -, where R ¹ and R ² , identical or different, each represent, and independently one of the other a hydrogen atom or a linear or branched C-pCβ alkyl group, and where z represents an integer of value 0 or 1, with the proviso that when z is 0, X does not represent -C (R ¹ ) (R ² ) -, the repeating units A1 being separated from each other by: α1) one or more hydrocarbon chains in d-Cioo _> preferentially in C ₆ -C ₁₀ O ₀ , saturated or unsaturated, linear or branched, different or identical, optionally containing one or more hydrocarbon rings, one or more aromatic and / or heterocyclic rings, and / or

α2) one or more alkylene oxide chains, for example ethylene oxide, propylene oxide or butylene oxide, with at least 2, preferably 5 repeating units, and

β) at least one associative group B.

The term "associative group" denotes any group capable of forming associative bonds by non-permanent (i.e. reversible) physical interactions, for example ionic bonds, hydrogen bonds, ion-dipole interactions. , dipole-dipole interactions, etc. The presence of such associative groups in the polycondensates described above makes possible the construction of supramolecular structures defined above. In the present invention, the term "associative bonds" preferably denotes hydrogen bonds, and most preferably hydrogen bonds between one or more nitrogenous groups.

The polycondensates that can be used in the present invention are characterized by the number of repeating units A1, as well as the number of associative groups B. Preferably, the ratio (number of repeating units A1) / (number of associative groups B) is different from 0, preferentially strictly greater than 0 and less than 200, more preferably between 0.1 and 100, even more preferably between 0.2 and 50, and advantageously between 0.3 and 20.

Although A1 is also capable of forming one or more associative bonds (for example when A1 is an amide repeating unit), the repeating units A1 are not counted as group B to determine the ratio defined above characterizing the polycondensates employed in the present invention.

In addition, the polycondensates used in the present invention have a weight average molecular weight (Mw) of between 200 daltons and 1000 kilodaltons, preferably between 1000 daltons and 500 kilodaltons, more preferably between 2000 daltons and 100 kilodaltons.

The polycondensates according to the present invention comprise two or more repeating units A1, which may be identical or different. Preferred polycondensates include A1 repeating units where z is 1 and X is -C (R ¹ ) (R ² ) - (polyamide repeating units), and / or where z is 0 and X is an atom of oxygen (polyester repeating units), and / or where z is 1 and X is oxygen (polyurethane repeat units), and / or where z is 1 and X is -N (R) ¹ ) - (patterns of polyurea repetition). The polycondensates that can be used in the bituminous compositions according to the present invention can be homopolymers, block copolymers or random copolymers. The polycondensates of polyamide type are particularly preferred, and more particularly the polyamides where -C (R ¹ ) (R ² ) - can be written as -CH ₂ - (that is to say, R ¹ = R ² = H) .

In a preferred embodiment, the polycondensate used in the present invention includes the reaction product (s) of the polycondensation of one or more monomers of carboxylic acid type di-, tri- or poly-functionalized with a or a plurality of di-, tri- or poly-functionalized amine monomers, such as, for example, one or more di-, tri- or poly-functional carboxylic acids, one or more di-, tri- or poly-functional amines, and their mixtures.

The resulting polycondensate is a polyamide, which can be obtained according to a conventional polycondensation reaction known to those skilled in the art. The resulting polyamide can react further with at least one compound comprising at least one associative group B, for example at least one compound consisting of one or more of the associative groups B as defined above, where the polycondensate can be prepared in presence of at least one compound comprising at least one associative group B, for example at least one compound comprising one or more associative groups B as defined above. In the latter case, it is understood that the compound or compounds comprising at least one associative group B are brought into contact with the monomers during the polycondensation reaction.

In another embodiment, the polycondensate used in the present invention includes the reaction product or products of the polycondensation of one or more monomers of carboxylic acid type di-, tri- or poly-functionalized with a or a plurality of di-, tri- or poly-functionalized alcohol monomers, such as, for example, one or more di-, tri- or polyfunctional carboxylic acids, one or more di-, tri- or polyfunctional alcohols, said polycondensate (which is a polyester) which can further react with, or be developed in the presence of, at least one compound comprising at least one associative group B, as described above.

In a further embodiment, the polycondensate used in the present invention includes the reaction product or products of the polycondensation of one or more isocyanate-type monomers di-, tri- or poly-functionalized with one or more several di-, tri- or poly-functionalized amine monomers and / or alcohol, such as, for example, one or more di-, tri- or polyfunctional aliphatic or aromatic isocyanates, and one or more a plurality of di-, tri- or polyfunctional alcohols, amines and / or aminoalcohols, said polycondensate (which is a polyurethane or a polyurea) which can further react with, or be prepared in the presence of, at least one compound comprising at least one associative group B, as described above.

Preferably, the polyfunctional carboxylic acids which may be employed in the reaction for obtaining the polycondensate according to the invention are chosen from saturated or unsaturated fatty carboxylic acids containing at least 8 carbon atoms, such as linear diacids such as suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, thapsonic acid (hexadecanedioic acid) or octadecanedioic acid, branched diacids, and more preferentially the fatty acid mixture (s) containing one or more dimers or trimers resulting from the oligomerization of unsaturated fatty acids of vegetable origin, such as myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic or docosenoic acids (extracts of pine, tall oil, corn, sunflower, soybean, rapeseed, grapes, flax or jojoba) or gold animal origin such as eicosapentaenoic or docosahexenoic acids (fish oil extracts), as well as mixtures thereof.

Preferred examples of carboxylic acids include fatty acids comprising unsaturated molecules, for example of the oleic type, which can be oligomerized by a condensation reaction of the double bonds. This reaction makes it possible to form mixtures consisting essentially of dimers and trimers, although small amounts of higher order oligomers, such as tetramers and pentamers, may be present. The terms "dimers and trimers of fatty acids" refer to oligomers formed from 2 or 3 identical or different monomers. Advantageously, these saturated or unsaturated fatty acids comprise between 12 and 100 carbon atoms, and more advantageously between 21 and 90.

Oligomeric mixtures of fatty acids generally comprise a given ratio of dimers and trimers of fatty acids. The proportion of fatty acid monomer and higher order oligomers (tetramers, pentamers, etc.) is low compared to that of fatty acid dimers and trimers.

Examples of dimer and trimer fatty acid molecules, representing the cyclic dimer and trimer of the fatty acid having 18 carbon atoms, Ci ₈ , are presented below. Commercial products are mixtures of isomers of such compositions, including also partially or fully hydrogenated structures.

C ₃ β cyclic fatty acid dimer

Cyclic fatty acid trimer in C ₅₄

[0046] A preferred blend of fatty acid oligomers consisting of dimers, trimers and monomers of the fatty acid Cl ₈ (linear or cyclic). An even more preferred mixture consists of:

Between 0.1 and 40% by weight, more preferably between 0.1 and 10% by weight of identical or different fatty acid monomers;

between 0.1 and 99.8% by weight, more preferably between 18 and 98% by weight of identical or different fatty acid dimers; and

between 0.1 and 99% by weight, more preferably between 2 and 80% by weight of identical or different fatty acid trimers.

[0047] Examples of dimers mixture of commercial fatty acids trimers include: Uniqema Pripol ^® 1017 products, Pripol ^® 1048, Pripol ^® 1013, Pripol ^® 1040, Pripol ^® 1009 and Pripol ^® 1006, Arizona Chemicals Products Unidyme ^® 60, Unidyme ^® 40 and Unidyme ^® 14, Cognis Empol ^® 1008, Empol ^® 1018, Empol ^® 1043, Empol ^® 1045, Empol ^® 1016 and Oleon products such as Radiacid ^® 0980 and Radiacid ^® 0950. , Pripol ^®, Unidyme ^®, Empol ^®, and Radiacid ^®, comprise fatty acid monomers -C ₈ and multiple oligomers of C _8.

Preferably, the polyfunctional amines that can be used in the polycondensation reaction to obtain the polycondensate used in the present invention are saturated or unsaturated polyamines containing at least 6 carbon atoms, such as linear diamines such as hexamethylenediamine. aromatic diamines such as phenylenediamine, and more preferably amines obtained by ammoniation (conversion of carboxylic groups to nitrile groups) and hydrogenation of fatty acids having at least 8 carbon atoms, such as the polyfunctional carboxylic acids described above, and mixtures thereof.

The preferred examples of polyfunctional amines derived from polyfunctional carboxylic acids are those resulting from the ammoniation and hydrogenation of dimers and trimers of fatty acids, such as those described in WO 2008/053113. Amino commercial polyfunctional like Versamine ^® Cognis, can also be used to develop polycondensates used in the present invention.

In another embodiment of the invention, the polyfunctional organic amines may be polyetheramines such as polypropylene oxide diamines and / or polyethylene. Commercial examples of such diamines include Jeffamine ^® D400, Jeffamine ^® D2000 and D4000 Jeffamine ^® marketed by Huntsman.

Preferably, the polyfunctional alcohols that can be used in the polycondensation reaction to obtain the polycondensate used in the present invention are saturated or unsaturated diols, linear or branched, preferably having at least 6 carbon atoms, such as the hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, dodecanediols (typically hexane-1,6-diol, heptane-1,7-diol, octane-1,8-diol, nonane-1, 9-diol, decane-1, 10-diol, 1,1-diund-1,1-diol, dodecane-1,12-diol), aromatic diols such as resorcinol, hydroquinone, bisphenol A, branched diols such as 1,6-hexylene glycol, and mixtures thereof, and more preferably alcohol mixtures containing one or more dimer or trimers resulting from the hydrogenation of oligomerized unsaturated fatty acids, such as those described above, as well as mixtures thereof.

In another embodiment of the invention, the polyfunctional alcohols may be oligomers or polymers of one or more alkylenediols, for example polyethylene glycol, ethylene glycol or butylene glycol, as well as their mixtures.

Preferably, the polyfunctional isocyanates that can be used in the polycondensation reaction to obtain the polycondensate used in the present invention are saturated or unsaturated diisocyanates, linear or branched, having at least 6 carbon atoms, such as aliphatic diisocyanates. or cycloaliphatic, preferably 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethanediisocyanates, 1,4-cyclohexanediisocyanate, bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as toluene-2,4-diisocyanate, toluene 2,6-diisocyanate, 4,4'-methylenediphenyldiisocyanate, 2,4'-methylenediphenyldiisocyanate, para-phenyl diisocyanate, naphthalene-1,5-diisocyanate or NPDI (isophorone diisocyanate), etc., and as their mixtures. As described above, the polycondensate used in the present invention comprises at least one associative group, covalently bonded to said polycondensate by reaction of said polycondensate, or reaction of the monomers of the polycondensate, with at least one compound comprising at least one functional group. T and at least one group B capable of forming associative bonds, preferably hydrogen bonds, said groups T and B being covalently bound to one another via at least one, and preferably to one (1) spacer group Sp.

In compounds comprising at least one T group, at least one B group and at least one Sp group, the functional group T may be any reactive chemical function capable of forming a covalent bond with the polycondensate and / or the monomers of said polycondensate, and such a function is preferably chosen from amine, alcohol, thioalcohol, halogen, carboxylic acid, thiocarboxylic acid, carboxylic acid anhydride, thiocarboxylic acid anhydride, carboxylic acid halide, halogenide, thiocarboxylic acid, isocyanate, epoxide, sulfonic acid, etc., the functions amino, alcohol and carboxylic acid being most preferred.

It is understood that the covalent bonds formed by the reaction of the group T with the polycondensate and / or the monomers of said polycondensate are not counted in the calculation of the total number of repeating units A1 present in the polycondensate as defined above. before.

The spacing group or groups Sp make it possible to bind the group (s) T to the group (s) B and may be of any nature known to those skilled in the art.

By way of nonlimiting examples, the spacer group Sp is preferably chosen from linear, branched or cyclic C ₁ -C ₂₀ hydrocarbon-based chains, optionally comprising one or more double and / or triple bonds, one or more aromatic rings and / or one or more heteroatoms. Said hydrocarbon chains may be substituted.

According to a preferred aspect of the invention, the spacer group Sp is a linear or branched C-pCβ hydrocarbon chain.

The group B capable of forming associative bonds, preferably hydrogen bonds, is a nitrogen group capable of forming non-permanent (ie reversible) physical interactions, for example ionic bonds, hydrogen bonds , ion-dipole interactions, dipole-dipole interactions, etc. Preferably, the group B is chosen from the groups B1 to B7:

(B1) (B2) (B3) (B4)

(B5) (B6) (B7)

where Z represents an oxygen atom, a sulfur atom or a -NH group, preferably an oxygen atom, and R represents any substituent group, for example a linear or branched C ₁ -C ₁₀ 0 alkyl group.

Compounds comprising at least one T group, at least one Sp spacer group and at least one B group may for example be represented by any one of the following formulas (1a) to (1f):

B T

T-Sp-B T B T βv B

(1a) (1b) (1c)

T T B

T Sp B T Sp T T Sp B

B B B

(1d) (1e) (1f)

It is understood that when several T groups are present, these groups may be identical or different. Similarly, when several B groups are present, and respectively several Sp spacer groups are present, they may be identical or different.

In a general and nonlimiting manner, the compounds (1a) to (1f) above preferably comprise a maximum of 4 T groups, and / or a maximum of 4 B groups. They comprise 1, 2 or 3, preferentially 1, spacer groups Sp.

According to a preferred embodiment, the compound corresponds to formula (1a) above. Nonlimiting examples of compounds that can react with the polycondensate, or the monomers of said polycondensate, include 1- (2-aminoethyl) imidazolidin-2-one (UDETA), 1- (2 - [(2- aminoethyl) amino] ethyl) imidazolidone (UTETA), 1- (2- {2 - [(2-aminoethylamino] ethyl} amino) ethyl] imidazolidone (UTEPA), N- (6-aminohexyl) -N '- ( 6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), 3-amino-1,2,4-triazole (3-ATA) and 4-amino-1,2 4-triazole (4-ATA), and mixtures thereof UDETA is preferred for use in the present invention.

All the compounds described above which comprise at least one group T, at least one group Sp and at least one group B are either known per se and commercial, or easily synthesized according to procedures known to those skilled in the art. , or available in the scientific literature, patents, Chemical Abstracts or on the Internet.

By way of example, the UDETA, UTETA and UTEPA compounds can be synthesized by reaction of urea with, respectively, diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).

The preferred examples of compounds comprising the preferred groups B3 to B6 described above correspond to the product of the reaction of urea with groups comprising NH ₂ or NH functions separated by 2 or more atoms, preferably by 2 or 3 carbon atoms, and more precisely the reaction of urea with amines, alkyleneamines, aminoalcohols or amidoamines. Examples of the reaction result of urea with a polyalkylamine include:

UDETA: 2-aminoethylimidazolidin-2-one or 1- (2-aminoethyl) imidazolidin-2-one, obtained by reaction of urea with diethylenetriamine (DETA);

UTETA: 1- (2 - [(2-aminoethyl) amino] ethyl) imidazolidin-2-one, obtained by reaction of urea with triethylenetetramine (TETA);

UTEPA: 1- (2- {2 - [(2-aminoethylamino] ethyl} amino) ethyl] imidazolidin-2-one, obtained by reaction of urea with tetraethylenepentamine (TEPA).

The other examples of compounds of formula B3 to B6 above include those obtained by reaction of urea or thiourea with:

Polyamines such as dipropylenetriamine, di- (1, 2-butylene) triamines, di- (2,3-butylene) triamines, N-methyldiethylenetriamines, N-ethyldiethylenetriamines and tripropylenetetramines;

amino alcohols such as 2 - [(2-aminoethyl) amino] ethanol.

The non-limiting examples of structural compounds of preferred formula B1 or B2 include respectively 4-amino-1,2,4-triazole and 3-amino-1,2,4-triazole. In another aspect, the present invention relates to the polycondensates defined above comprising at least two repeating units A1 and at least one associative group B, provided that the ratio of the total number of said repeating units to the number total groupings B is different from 0.

Such polycondensates, which form a further aspect of the present invention, are produced according to any method known to those skilled in the art, as described above, and for example according to any known method for producing conventional polycondensates, by reacting at least one additional compound comprising at least one group T, at least one group B and at least one group Sp, so that the functional group or groups T form a covalent bond with the polycondensate and / or the monomers said polycondensate.

Non-limiting examples of such polycondensates according to the present invention include those obtained by reaction of the following compounds:

fatty acid oligomer, amine derived from the ammoniation of a fatty acid oligomer and UDETA;

fatty acid oligomer, amine derived from the ammoniation of a fatty acid oligomer and UTETA;

fatty acid oligomer, amine derived from the ammoniation of a fatty acid oligomer and 4-amino-1,2,4-triazole;

Fatty acid oligomer, linear diamine comprising 10 carbon atoms and UDETA; fatty acid oligomer, linear diamine of propylene oxide and UDETA;

fatty acid oligomer, linear diamine of propylene oxide / ethylene oxide and UDETA; sebacic acid, amine from the ammoniation of a fatty acid oligomer and UDETA; fatty acid oligomer, a mixture of an amine derived from the ammoniation of a fatty acid oligomer and a linear diamine containing 10 carbon atoms and UDETA;

fatty acid oligomer, a mixture of an amine derived from the ammoniation of a fatty acid oligomer and a linear diamine of propylene oxide and UDETA;

suberic acid, amine derived from the ammoniation of a fatty acid oligomer and UDETA; fatty acid oligomer, decanediol and UDETA;

Fatty acid oligomer, polypropylene glycol and UDETA;

suberic acid, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

sebacic acid, polypropylene glycol and UDETA;

fatty acid oligomer, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA; fatty acid oligomer, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UTETA;

fatty acid oligomer, mixture of decanediol and an alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

Hexamethylenediisocyanate, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

toluenediisocyanate, an alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

toluenediisocyanate, an alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UTETA;

hexamethylenediisocyanate, a mixture of decanediol and an alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

toluene diisocyanate, polypropylene glycol and UDETA.

According to a particularly preferred embodiment, the examples of polycondensates useful for the invention are those obtained by the reaction of a dimer / trimer of fatty acid, a diamine resulting from ammoniation and from hydrogenation of a dimer / trimer of fatty acid and 2-aminoethylimidazolidin-2-one (UDETA) as a compound comprising the group capable of forming the supramolecular structure, thereby obtaining the following polyamide, of which the structure can be schematically represented by the figure below:

where a, b, c, d, e, f, g and h are between 1 and 24, preferably between 2 and 20 and even more preferably between 4 and 16, m represents an integer whose value is greater than or equal to 1 and less than 2000.

[0075] One of the other examples of polycondensate according to the present invention which is useful for the bituminous compositions of the present invention is that obtained by the reaction of a dimer / trimer of fatty acid, of a diol resulting from hydrogenation. a dimer / trimer fatty acid and 2-aminoethylimidazolidin-2-one (UDETA), which allows to obtain the following polyester, which can be schematically represented by the structure below:

where a, b, c, d, e, f, g, h and m are as defined above.

One of the additional examples of polycondensate according to the present invention that can be used in the bituminous compositions of the present invention is that obtained by the reaction of a linear saturated diisocyanate, a diol resulting from hydrogenation. a dimer / trimer fatty acid and 2-aminoethylimidazolidin-2-one (UDETA), which allows to obtain the following polyurethane, which can be schematically represented by the structure below:

where a, b, c, d, e, f, g, h, m are as defined above, and i is between 4 and 20.

The polycondensate employed in the invention may also result from the reaction involving other fatty acid derivatives, such as a fatty acid ester or a fatty acid chloride. One of the preferred fatty acid esters is a fatty acid methyl ester, particularly a methyl ester of a fatty acid dimer or a mixture of fatty acid oligomers as previously described. One of the examples of fatty acid chloride is sebacoyl chloride.

The polycondensate used in the invention may optionally be produced in stoichiometric proportion. For example, in the case of a dimer / trimer acid, a dimer / trimer amine and UDETA, the total number of reactive amino groups (dimer amine / trimer and UDETA) can be adjusted to be in stoichiometric proportion. to fatty acids, which means an amine (or UDETA molecule) for each grouping acid of the fatty acid, or in non-stoichiometric proportion, which means an excess or a lack of amines relative to the acidic groups.

The present invention also encompasses the fact of chemically cross-linking the polycondensate by using a crosslinking agent before, or more preferably after the development of the bituminous composition. Examples of such crosslinking agents include urea, sulfur or sulfur molecules such as di-ferf-dodecyl pentasulfide.

The content of the polycondensate (s) within the present invention is preferably included in the range 0.05 parts by weight to 20 parts by weight per 100 parts by weight of the bitumen or bitumens. Less than 0.05 parts by weight of polycondensate does not provide the desired effects. A polycondensate content greater than 20 parts by weight would be compatible with the object of the present invention; the upper limit of 20 parts by weight is established only for economic reasons. Expected effects could also be achieved with contents greater than 20 parts by weight, or even greater than 30 parts or 40 parts by weight.

The bituminous composition according to the present invention may be in the form of an aqueous emulsion, the amount of water generally being between 10% by volume and 70% by volume relative to the total volume of the emulsion.

The polycondensates described above surprisingly exhibit a low viscosity in the temperature range at which the bitumen compositions are generally produced, while at the same time having good mechanical properties at the application temperatures (application on a road for example).

Without this being a limiting theory, one of the explanations of these properties may be the formation of associations or thermoreversible bonds between the polycondensates, mainly via the associative groups B present in the polycondensate. These associations are of the hydrogen bond type. The number of associations can be greater than two per molecule, resulting in the formation of a network to further improve the mechanical properties of low temperature polycondensate.

The bituminous composition according to the present invention offers a unique advantage vis-à-vis bitumens modified by conventional polymers in the manufacturing process. Normally, the dispersion of a conventional polymer in a bitumen requires the heating of the bitumen at higher temperatures (about 20 ⁰ C) at their normal storage temperature, long mixing times (usually several hours), as well as specific mixing devices under important shear conditions. In contrast to this, the production method of the present invention can be implemented at temperatures much closer to those to which the Pure bitumen is normally stored, with much shorter durations (several minutes) under moderate to low shear conditions.

The bituminous composition according to the present invention preferably has the structure of a dispersion or a solution. The term "dispersion" refers to a structure in two or more phases. A structure in two or more phases can be observed under an optical microscope thanks to the difference in refractive index, one phase being dispersed in the form of spheres in the other phase; the interface between the two phases is sufficiently well defined under the light microscope. The term "solution" denotes a monophasic object that does not show a sudden change in the refractive index within it, and therefore no defined shape.

When the bituminous composition according to the present invention has the structure of a dispersion, two cases are possible. In the first case of dispersion, the polycondensate is essentially present in a dispersed phase within the bitumen phase. It is also possible that in this dispersed phase, some components of the bitumen will swell said polycondensate component. In the second case of dispersion, the polycondensate is essentially present in the continuous phase. It is possible that some components of the bitumen will swell the above-mentioned polycondensate component. In this situation, the dispersed phase consists essentially of bitumen.

The two situations described above may be encountered depending on the content of said polycondensate component and the nature of the bitumen. It is important to adjust the structure of the bituminous composition to the application to optimize its performance. For example, bituminous compositions intended to be transported over long distances in a concentrated form of polycondensate, for economic reasons, advantageously include a dispersion of the swollen polymer in the continuous phase. For example, a dispersion containing dispersed elements that are not evenly distributed demonstrates poor storage stability.

According to another embodiment, the bitumen composition according to the present invention may further include at least one anionic, cationic, zwitterionic or amphoteric surfactant added to the bitumen or in the aqueous phase.

The bituminous composition according to the present invention may also comprise one or more other components, such as those commonly used in the field of bitumens and asphalts. These may include anti-stripping agents, usually anionic, cationic, zwitterionic or amphoteric surfactants. Non-limiting examples of such anti-stripping agents include: alkylcarboxylic acids, sulfated surfactants, sulfonated surfactants, alkyl- or arylcarboxylic acids, fatty acid esters of quaternary alkanolamines, alkylamidopolyamines, alkylimidazolines and alkylimidazopolyamines, the reaction products between the polyamines and the carboxylic fatty acids, the reaction products between the alkylpolyamines and the carboxylic fatty acids, and, in a similar way, the reaction products between the fatty acids or the vegetable oil and diethanolamine, followed by reaction with polyamines. Non-limiting examples of quaternary alkanolamine include betaine salts and N, N, N-trialkylcholine salts with strong inorganic or organic acids, such as, for example, methanesulfonic acid.

Nonlimiting examples of polyamines include the following compounds: dimethylaminopropylamine, N-aminoethylpiperazine, diethylenetriamine, triethylenetetramine and tetraethylene pentamine.

Other additives that can be advantageously added to the bituminous composition described in the present invention are chosen from:

polyphosphoric acid, including all the different grades and designations existing for polyphosphoric acids, including pyrophosphoric acid, triphosphoric and metaphosphoric acids and phosphonic acid,

pyrophosphates and other similar compounds comprising at least one (OH-) P = O group, such as those described in WO 2008/148974,

polymers generally used to improve the mechanical performance of bitumen and asphalt,

Paraffins, for example Fischer-Tropsch paraffins described in US Pat. No. 6,588,974,

fluxing agents,

esters of fatty acids and functionalized waxes,

dialkyldiamides, for example those mentioned in WO 2007/73378,

• Resin-type components, such as rosin acids, or modified rosin acids, talloil pitch, pine tar pitch, pine rosin, talloil rosin,

asphaltites, for example Gilsonite ^® ,

oils of vegetable or mineral origin and their derivatives,

• as well as mixtures of two or more additional additives.

Other additives that can be advantageously added to the bituminous composition described in the present invention are chosen from those used to reduce the temperature of production of a mix, for example those described in WO 2006/106222 and WO 2007/141458. .

According to a further aspect, the present invention also encompasses the addition of conventional polymers generally used to improve the mechanical performance. bitumen and blending, that is, commonly used in bitumen modification, such as: styrene-butadiene rubbers, styrene / butadiene block copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers , polyethylene and other alpha-polyolefins (as described in Asphalt binder testing manual, Asphalt Institute 2007) and porous rubbers.

All these additional components and additives may be added to the bituminous compositions by any known method. Generally, the overall content of said additional components and additives in the bituminous composition according to the present invention is between 0.01% and 30% by weight relative to the total weight of the bituminous composition.

In another aspect, the present invention relates to the process for preparing a bituminous composition comprising at least one polycondensate comprising at least one associative group B comprising at least the following steps:

adding from 0.05 to 20 parts by weight of the polycondensate defined above in the solid state, melted, dissolved or dispersed to 100 parts by weight of a bitumen at its standard storage temperature, depending on its class, as described in standard NF EN 13108-1 of February 2007,

possible addition, before or after the addition of the polycondensate, of one or more additives such as those described previously,

Mixing, preferably with moderate stirring, by any mechanical means, for a period generally of between 1 minute and several hours, typically between 1 minute and 60 minutes, and

obtaining a ready-to-use bituminous composition.

The bituminous composition obtained according to the above process can be produced at any stage of the supply chain, from the refinery to the mixer of the mixing unit, and can be used as it is or in admixture with mineral aggregates to obtain mixes.

According to another embodiment, the polycondensate, in the molten or dissolved state, can be added to a continuous flow of the bitumen by any known means, for example by direct injection or direct injection and static mixer.

In another aspect, the above method is used to obtain an aqueous bitumen emulsion comprising the polycondensate, the water content generally ranging between 10 and 70% by volume relative to the total volume of the emulsion. . In this case, the bituminous composition is mixed with an aqueous phase containing one or more emulsifiers, such as those commonly employed by those skilled in the art, with a static mixer or a mobile mixer, or a combination of both. According to another aspect, the present invention relates to a formula comprising at least one polycondensate as defined above, and at least one or more additives, such as those listed above, typically selected from anti-stripping agents, polyphosphoric acid, the additives described in WO 2008/148974, the paraffins, for example the Fischer-Tropsch paraffins described in US Pat. No. 6,588,974, the fatty acid esters and the functionalized waxes, the dialkyldiamides, for example those mentioned in WO 2007 / 073378, resin components such as rosin acids, talloil pitch, pine tar pitch, pine rosin, talloil rosin, asphaltites, eg Gilsonite ^® , conventional polymers, porous rubber, vegetable or mineral oils and their derivatives, as well as those used to reduce the temperature of production of a mix described in WO 2006/106222 and WO 2007/1414 58.

Depending on the nature of the polycondensates and additives, it is possible that such formulas do not exhibit satisfactory storage stability. In such cases, the formulas defined above may advantageously be in the form of a two-part component, for example the polycondensate (s) on one side, and the additive (s) on the other, or alternatively, the polycondensate (s) with some of the additives on one side, and the rest of the additives on the other side.

The main application of the polycondensates, formulas and bituminous compositions including them, as presented in the present invention, is the manufacture of asphalt for the coating of road surfaces, typically for the construction of roads, car parks, airport runways or any similar drivable surface. Other applications of the bituminous compositions according to the present invention include waterproofing applications, for example the waterproofing of roofs, terraces, walls, etc., as well as applications in adhesive formulations.

The bituminous composition described in the present invention as well as the resulting mix produced from said bituminous composition have, surprisingly, improved mechanical properties compared to the bituminous compositions and the mixes described in the literature.

Thus, and according to a further aspect, the present invention relates to a surface coated in whole or in part with a bituminous composition as described above and / or an asphalt as defined above, said surface generally being a road surface, for example example, a road, a parking lot, a bridge, an automobile lane or a motorway, an airport runway or any other similar vehicular surface, as well as any surface requiring asphalt or asphalt pavement, for example asphalt, sidewalk, a playground, a roof, a terrace, a wall etc. The mineral aggregates used with the bituminous composition according to the present invention to manufacture a mix are not limited in their chemical nature, their shape or their size and can be obtained in quarries, recovered from previous mixes (milling costs). coated or RAP, for example defined in the French standard AFNOR XP P98-135 of December 2001), the building demolition products and the mixture of any of the elements above. Asphalt prepared with the bituminous composition presented in the present invention may contain other common components of the mixes, such as organic fibers (for example: cellulose, cotton, polypropylene, polyester, polyvinyl alcohol and polyvinyl alcohol fibers). polyamide) and inorganic fibers (for example: glass, metal or carbon fibers).

In one of the embodiments of the invention, the bituminous composition is employed in the known techniques of bonding layer, surface mix, in the treatment of surfaces, the impregnation of surfaces, the Roof covering or roofing membranes, waterproofing with anhydrous bitumen compositions or in emulsion form.

The bituminous composition described in the present invention can be used in any method of manufacturing asphalt, such as those employing the addition of a bituminous emulsion, the addition of hot bitumen, or any which of the various processes for manufacturing hot or semi-hot mixes (where the manufacturing temperature is greater than ambient temperature but lower than that of a conventional hot mixing process), such as bitumen foaming techniques, for example US 2008/00259714 which discloses a special foaming device associated with multi-stage heating and a drying and mixing device, US 5,910,212 and WO 97/20890 which use a hard bituminous binder combined with the mixture of a bituminous binder soft and aggregates, or US 2005/0076810 which employs an additive of high desorption capacity, or EP 1 469 038 where a portion of the aggregates is heated, dried and mixed bitumen before being mixed with wet aggregates, or US 2006/00236614 where the aggregates are dried and mixed with the bitumen but with a drying step, so that a fraction of the initial moisture of the aggregates is retained, or WO 07/112335 which uses a dispersion of water-in-oil bitumen with specific surfactants, or US Pat. No. 6,588,974 which uses a Fischer-Tropsch paraffin added to the bitumen, in combination or as a partial or total replacement of the mentioned bitumen.

The bituminous composition described in the present invention provides advantages over conventional methods for manufacturing water / bitumen or bitumen / water emulsions with bitumens modified with conventional polymers. The reduced viscosity at low temperature makes it possible to develop emulsions with modified bitumen according to the present invention at lower temperatures and pressures. Lower penetration bitumen grades may be employed.

According to another aspect, the present invention relates to the process for preparing an asphalt mix where the polycondensate in a solid, molten, dissolved or dispersed state is added to the mineral aggregates before, at the same time as, or after, adding the bitumen or bituminous composition in the mixing process.

This also applies to other components and additives that can be added to the asphalt composition: anti-stripping agents, polyphosphoric acid, paraffins, for example Fischer-Tropsch paraffins described in US 6,588,974, fatty acid esters. and functionalized waxes, dialkyldiamides such as for example those mentioned in WO 2007/073378, resin-type components, such as rosin acids, talloil pitch, pine tar pitch, pine rosin, talloil rosin, Gilsonite ^® , fluxing agents, conventional polymers, porous rubber, vegetable or mineral oils and their derivatives, as well as those used to reduce the production temperature of a mix described in WO 2006/106222, WO 2007/141458 and WO 2008/148974.

The process for producing a mixture above can advantageously be implemented when the bituminous composition according to the invention is in the form of an aqueous emulsion.

The present invention also confers several advantages in terms of manufacturing, laying and compaction of the mixes produced by hot mixing. The manufacture of an asphalt mix according to the invention by hot mixing can be carried out at temperatures similar to those generally used for pure bitumen. This is generally not possible with conventional polymer modified bitumens, since a considerable increase in viscosity is observed when cooled from the preparation temperature to the temperature at which pure bitumen is generally stored (difference of about 20 ⁰ C). An increase in viscosity results in a difficult or incomplete coverage of the mineral aggregate by the modified bitumen.

This increase in viscosity would also have a negative impact on the laying and compaction of the mix. In the mixes made with the bituminous composition presented in the invention, no particular problem related to the viscosity increase can take place, because it remains similar to that of pure bitumen at the manufacturing, laying and compacting temperatures.

In addition, the manufacture of an asphalt mix with the bituminous composition presented in the invention can be implemented at temperatures lower than those generally used for pure bitumens, for example less than those at which pure bitumen is commonly stored. . Such mixes can also be laid and compacted at lower temperatures because they have a higher fluidity than asphalt mixes made from conventional polymer modified bitumen, while improving the mechanical properties of the mixture under the final application conditions.

The reduction in manufacturing temperature by using the bituminous compositions according to the invention would result in a reduction of the energy consumed during the manufacture of the mix, the mineral aggregates do not need to be heated as much as in manufacturing involving a conventional modified bitumen. In addition, this reduction of energy also implies a reduction in CO ₂ and other greenhouse gas emissions, as well as a reduction in the oxidation of bitumen and polymers.

One of the other advantages of the present invention when it is used to manufacture a mix is its ease of recycling, compared to the mixtures made from conventional polymer modified bitumen, particularly with cross-linked mixtures. chemically, because once heated, the fluidity of the mix comprising the bituminous composition according to the present invention is greater than equal temperature, which facilitates the steps of handling, flow, mixing and compaction.

The present invention will now be illustrated by means of the following examples, which do not limit it in any way. Examples

Example of Preparation of Polycondensates Used in the Present Invention

In all the examples, the equivalent molar masses of the reagents are obtained by measurements of basicity for the amines and of acid number for the acids. Example 1

In a 500 cm ³ glass reactor provided with an adjustable speed stirring motor, inlets for introducing reagents, inert gases such as nitrogen and measuring probes (for example temperature probes), a steam condensation / extraction system that can be connected to a vacuum production system (vacuum pump, vacuum trap, etc.) and an envelope for heating or cooling the contents of the reactor by circulating a heat transfer fluid, for example the oil of a thermostated bath, 0.1 M (63 g) of a Pripol ^® 1040 fatty acid dimer are introduced and heated at 160 ^° C. with stirring and nitrogen atmosphere. Then, 0.14 M (18.8 g) of 1- (2-aminoethyl) imidazolin-2-one (UDETA) are added dropwise, and then the temperature is maintained at 160 ^° C. for 1 hour. [0119] 0.027 M (16.8 g) of Versamine ^® 551 (Cognis), total 3.25 basicity, are then added. The generated water is distilled and collected continuously through a Dean-Stark device. The reaction is continued until the distillation of the water is stopped. The polycondensate obtained is extracted from the reactor in the molten state.

The polycondensate obtained has a G ^* complex module of 1.1 MPa at 25 ° C., as measured on an Anton Paar Physica MCR301 rheometer at a stress of 1% at 1.6 Hz. The ratio of groups A1 B of the polycondensate obtained is calculated based on the molar amounts of Versamine 551 ^® and UDETA. The functionality of Versamine ^® 551 is arbitrarily set at 2 (the average functionality being greater than or equal to 2 because Versamine ^® is primarily a mixture of di- and tri-amines). UDETA has a group B per mole. The A1 / B ratio of the polycondensate of Example 1 is (0.027 ^* 2) 1 (0.14 ^* 1), i.e., 0.38.

Example 2

In a 500 cm ³ glass reactor provided with an adjustable speed stirring motor, inlets for introducing reagents, inert gases such as nitrogen and measuring probes (for example temperature probes), a steam condensation / extraction system that can be connected to a vacuum production system (vacuum pump, vacuum traps, etc.) and an envelope for heating or cooling the contents the reactor by circulating a heat transfer fluid, for example oil from a thermostated bath, 0.1 M (63 g) of a fatty acid dimer Pripol ^® 1040 are introduced and heated at 180 ⁰ C with stirring and nitrogen atmosphere. Then 0.055 M (9.53 g) of 1,10-decanediamine are added and the temperature is maintained at 180 ^° C for 30 minutes.

0.09 M (12 g) of UDETA are then added dropwise. The generated water is distilled and collected continuously through a Dean-Stark device. The reaction is continued for 4 hours at 180 ^° C. The polycondensate obtained is extracted from the reactor in the molten state.

The polycondensate obtained has a complex modulus G ^* of 0.23 MPa at 25 ° C. (measured in the same manner as in Example 1). A1 / N ratio is calculated as in Example 1, based on amounts of Pripol ^® 1040 and UDETA. The functionality of 1, 10-decanediamine is 2. The ratio A1 / B is (0.055 ^* 2) / (0.09 ^* 1), i.e. at 1.22. Example 3 [0124] Example 2 was repeated by varying the nature and amount of amine added with 0.06 M (34.9 g) of Versamine 551 ^® 3.44 total basicity. The temperature is then maintained at 180 ^° C. for 30 minutes. 0.08 M (10.7 g) of UDETA are then added dropwise. The generated water is distilled and collected continuously through a Dean-Stark device. The reaction is continued for 4 hours at 180 ^° C. The polycondensate obtained is extracted from the reactor in the molten state.

The polycondensate obtained has a G ^* complex module of 0.33 MPa at 25 ° C (measured in the same manner as in Example 1). A1 / B of the polycondensate obtained ratio is calculated, based on the introduced amounts of Versamine 551 ^® (functionality arbitrarily set to 2, as explained in Example 1) and UDETA, and is equal to (0.06 ^* 2) / (0.08 ^* 1), i.e. at 1, 5.

Example 4

[0126] In a reactor similar to those used in the preceding examples, 0.05 M (31, 5g) of a fatty acid dimer Pripol ^® 1040 are introduced and heated at 180 ⁰ C under stirring and an atmosphere of nitrogen. 0.04 M (166 g) of a polyether amine marketed under the name Jeffamine ^® D4000, total basicity of 0.48, is then added and the temperature was maintained at 180 ⁰ C for 30 minutes. 0.02 M (2.6 g) of UDETA are then added dropwise. The generated water is distilled and collected continuously through a Dean-Stark device. The reaction is continued for 4 hours at 180 ^° C. The polycondensate obtained is extracted from the reactor in the molten state.

The polycondensate obtained has a complex modulus G ^* of 0.001 MPa at 25 ° C. (measured in the same manner as in Example 1). The ratio A1 / B of the polycondensate obtained is calculated from the amounts of Jeffamine ^® D4000 (functionality = 2) and UDETA, and is equal to ^{(0.04 * 2) / (0.02} * 1) , c ' that is to say 4.

Example 5

As a comparative example, an organogel compound as described in US Pat.

FR 2 924 121, that is to say a compound containing no repeating unit A1 within the meaning of the present invention (ratio A1 / B = 0), is developed as follows: in a reactor similar to those of the examples 10,265 g of Empol ^® 1008, a dimer of fatty acid marketed by Cognis, and 5.2 g of UDETA are introduced and heated at 190 ° C. under stirring conditions and under a nitrogen atmosphere.

The water generated is distilled and continuously collected via a Dean-Stark device. The reaction is continued for 24 hours at 190 ^° C. The organogel obtained is extracted from the reactor in the molten state. The organogel obtained has a complex module G ^* of 0.21 MPa at 25 ° C, as measured on a Anton Paar Physica MCR301 rheometer under a 1% stress at 1.6 Hz.

Example 6

The complex viscosity of the polycondensates used in the present invention, developed as described in Examples 1 and 3, is measured on a dynamic shear rheometer (MCR 301 Anton Paar). The values of such parameters to 1, 6 Hz to 160 ⁰ C and 120 ⁰ C are shown in Table 1. The value of a poly (ethylene vinyl acrylate) pure (EVA 20/20) (Evathane 20 ^® / 20, Arkema) is also presented for comparison. It is observed that the viscosity of the polycondensates is significantly lower than that of the EVA, and is almost 2 orders of magnitude lower in the case of the polycondensate of Example 1 at both temperatures. The preparation of the bituminous composition according to the invention is very easily implemented because of this reduced viscosity.

- Table 1 -

Example 7

The development of a bituminous composition according to the invention is implemented by adding 5 parts of the polycondensate prepared as described in Example 1 in solid form to 100 parts of a TOTAL bitumen 35/50 penetration. The bitumen is preheated to 160 ^° C. and kept at this temperature under moderate stirring conditions (about 100 rpm) during the addition of the polycondensate. After adding the polycondensate, the mixture is stirred for 15 minutes to obtain a homogeneous mixture (Composition 1).

Example 8

The storage module G 'and the loss module G "of the composition described in Example 7 are measured on a dynamic shear rheometer (MCR 301 by Anton Paar) .The values of such parameters at 1, 6 Hz at 40 ° C., 60 ° C. and 80 ^° C. are presented in Table 2. For comparison, the values for pure 35/50 bitumen are also presented, It is observed that the bituminous composition according to the invention improves the values of the modules with respect to the pure bitumen The storage module according to the invention is between twice (40 ^° C.) and an order of magnitude (80 ^° C.) higher than that of pure bitumen. The loss module is also greater in the case of the bituminous composition according to the invention than in the case of pure bitumen.

- Table 2 -

Example 9

A bituminous composition is prepared by adding 5 parts of the polycondensate prepared as described in Example 3 in solid form in 100 parts of a TOTAL 35/50 penetration bitumen. The bitumen is preheated to 160 ° C and stored at this temperature under moderate agitation conditions (about 100 rpm) during addition of the polycondensate. After the end of the addition of the polycondensate, the mixture is stirred for 15 minutes to obtain a homogeneous mixture (Composition 2).

An asphalt mix is produced from this Composition 2. The following mineral aggregates of standard particle size for the construction of asphalt are used in this mix:

Calcium load 1, 5%

Sand 0/4 48,5%

Aggregate 4/6 14%

Aggregate 6/10 36%

Composition 2 is mixed with mineral aggregates at 160 ⁰ C, according to a conventional hot melt asphalt manufacturing process. The amount of composition 2 in the mix is 5.6% relative to the aggregates. The resulting mix is compacted on a gyratory press at 160 ^° C. The compacted sample is then cooled and kept at a constant temperature (20 ° C.) for 24 hours before testing.

[0136] A reference sample using pure 35/50 bitumen, and two comparison samples, one containing 100 parts of a 35/50 bitumen modified with 5 parts of a 20/20 EVA (Evathane ^® 20 / 20, Arkema), the other containing 5 parts of commercial polymer modified bitumen with SBS (SHELL), are treated identically. Indirect tensile tests were performed on all samples using a universal Instron testing machine in compression at a speed of 50 mm / minute. The values of the modulus of elasticity, obtained from the compression curves, are presented in Table 3. It is clear that in this case, the composition 2 has, surprisingly, a modulus significantly greater than that of the bitumen pure and comparable to those prepared with the SBS polymer. The composition according to the invention and that containing SBS have a higher modulus than that prepared with the EVA-modified bitumen. It is observed that a coating produced from the bituminous composition according to the invention makes it possible to obtain mechanical properties similar to those of bitumens modified with conventional polymers.

- Table 3 -

Example 10

Indirect tensile strength ratios (ITSR) are measured according to ASTM standard D4867 (conditioning at 60 ^° C. for 1 day) on the mixes prepared in Example 9. A sample made with 35/50 pure bitumen was also analyzed for reference.

In addition, an ITSR test was also carried out on the mixes prepared according to the procedure of Example 9, comprising a bituminous composition containing the organogel compound of Example 5 (Composition 3) to demonstrate the advantages of the present invention. This Composition 3 was made by adding 5 parts of the organogel compound of Example 5 to 100 parts of a TOTAL 35/50 penetration bitumen. The bitumen is preheated to 170 ^° C. and kept at this temperature under moderate stirring conditions (about 100 rpm) during the addition of the organogel. After the end of the addition of the organogel, the mixture is stirred for 2 hours to obtain a homogeneous mixture.

Table 4 below shows the ITSR ratios between the breaking force of a sample of the mix tested after being stored under dry conditions and a second stored under water at 60 ° C for one day.

- Table 4 -

It is observed that the sample prepared with the compound of Example 5 decreases NTSR of the mix, which makes it more sensitive to damage due to moisture. In contrast, the sample prepared with composition 2, a polycondensate according to the present invention, not only decreases this value, but also surprisingly increases it. This demonstrates a clear advantage of the bituminous compositions according to the present invention compared to other bituminous compositions comprising molecules bearing associative groups similar to that described in Comparative Example 5.

Claims

claims

A bituminous composition comprising at least one bitumen and at least one polycondensate comprising one or more associative groups.

The bituminous composition of claim 1, wherein said one or more polycondensates comprises:

α) at least two repeating units of formula (A1):

where X represents an oxygen atom, a group -C (R ¹ ) (R ² ) -, or a group -N (R ¹ ) -, where R ¹ and R ² , identical or different, each represent, and independently from each other a hydrogen atom or a linear or branched dC ₆ alkyl group, and where z represents an integer of 0 or 1, with the proviso that when z is 0, X does not represent -C (R ¹ ) (R ² ) -, the repeating units A1 being separated from each other by: α1) one or more hydrocarbon chains in d-Cioo _> preferentially in C ₆ -Ci ₀ O, saturated or unsaturated, linear or branched, different or identical, optionally containing one or more hydrocarbon rings, one or more aromatic and / or heterocyclic rings, and / or

β) at least one associative group B. 3. Bituminous composition according to any one of claims 1 or 2, wherein the one or more polycondensates comprise at least two repeating units A1 and at least one associative group B, the ratio A1 / B being different from 0, preferably strictly greater than 0 and less than 200, more preferably between 0.1 and 100, even more preferably between 0.2 and 50, and advantageously between 0,

3 and 20.

4. Composition bituminous material according to any one of claims 1 to 3, wherein the or polycondensates have an average molecular weight (M _w) between 200 daltons and 1000 kilodaltons, preferably between 1,000 daltons and 500 kilodaltons, more preferably between 2000 daltons and 100 kilodaltons.

5. bituminous composition according to any one of claims 1 to 4, wherein the polycondensate or polycondensates are homopolymers, block copolymers or random copolymers, having repeat units amide, ester, urethane or urea, and preferably, the or the polycondensates are polyamides.

6. Bituminous composition according to any one of the preceding claims, in which the associative group (s) B of the polycondensate (s) are chosen from:

(B1) (B2) (B3) (B4)

(B5) (B6) (B7)

where Z represents an oxygen atom, a sulfur atom or a -NH group, preferably an oxygen atom, and R represents any substituent group, for example a linear or branched C ₁ -C ₁₀ alkyl group.

Bituminous composition according to any one of the preceding claims, wherein the content of the polycondensate (s) is between 0.05 parts by weight and 20 parts by weight per 100 parts of the bitumen (s).

8. bituminous composition according to any one of the preceding claims, which is in the form of a dispersion, a solution or in the form of an aqueous emulsion, in which the amount of water is between 10% in volume and 70% by volume of the total volume of the emulsion.

9. Process for producing a bituminous composition according to any one of the preceding claims, comprising at least the following steps: adding from 0.05 to 20 parts by weight of the polycondensate defined above in the solid state, melted, dissolved or dispersed to 100 parts by weight of a bitumen at its standard storage temperature, depending on its class, as described in standard NF EN 13108-1 of February 2007,

• any addition, before or after the addition of the polycondensate, of one or more additives such as those described previously,

Obtaining a ready-to-use bituminous composition.

A polycondensate capable of forming a supramolecular structure comprising: α) at least two repeating units of formula (A1):

where X represents an oxygen atom, a group -C (R ¹ ) (R ² ) - or a group -N (R ¹ ) -, where R ¹ and R ² , which are identical or different, each represent, and independently, one of the other a hydrogen atom or a linear or branched C-pCβ alkyl group, and where z represents an integer of value 0 or 1, with the proviso that when z is 0, X does not represent -C (R ¹ ) (R ² ) -, the repeating units A1 being separated from each other by: α1) one or more hydrocarbon chains in d-Cioo _> preferentially in C ₆ -Ci ₀ O, saturated or unsaturated, linear or branched, different or identical, optionally containing one or more hydrocarbon rings, one or more aromatic and / or heterocyclic rings, and / or

β) at least one associative group B.

11. Polycondensate according to claim 10, wherein the ratio A1 / B is different from 0, preferably strictly greater than 0 and less than 200, more preferably between 0.1 and 100, even more preferably between 0.2 and 50. and advantageously between 0.3 and 20.

12. A polycondensate according to any one of claims 10 or 11, average molecular weight (M _w) between 200 daltons and 1,000 kilodaltons, preferably between 1000 daltons and 500 kilodaltons, more preferably between 2000 daltons and 100 kilodaltons.

13. Polycondensate according to any one of claims 10 to 12, which is a homopolymer, a block copolymer or a random copolymer, comprising repeat units amide, ester, urethane or urea, and which is preferably a polyamide.

14. Polycondensate according to any one of claims 10 to 13, wherein the associative group (s) B are chosen from:

(B1) (B2) (B3) (B4)

(B5) (B6) (B7)

15. Polycondensate according to any one of claims 10 to 14, obtained by the reaction of the following compounds:

fatty acid oligomer, linear diamine having 10 carbon atoms and UDETA; fatty acid oligomer, linear diamine of propylene oxide and UDETA;

fatty acid oligomer, polypropylene glycol and UDETA;

sebacic acid, polypropylene glycol and UDETA;

fatty acid oligomer, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

fatty acid oligomer, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UTETA;

Toluenediisocyanate, alcohol oligomer derived from the hydrogenation of a fatty acid oligomer and UDETA;

toluene diisocyanate, polypropylene glycol and UDETA.

16. Polycondensate according to any one of claims 10 to 15, obtained by the reaction of the following compounds:

Dimer / trimer of fatty acid, diamine resulting from the ammoniation and hydrogenation of a dimer / trimer of fatty acid and UDETA, or

dimer / trimer of fatty acid, diol derived from the hydrogenation of a dimer / trimer of fatty acid and UDETA, or

linear saturated diisocyanate, diol derived from the hydrogenation of a fatty acid dimer / trimer and UDETA.

17. Formulation comprising at least one polycondensate according to any one of claims 10 to 16, and at least one or more additives chosen from anti-stripping agents, polyphosphoric acid, pyrophosphates and other similar compounds comprising at least one grouping (HO) P = O, paraffins, fatty acid esters and functionalized waxes, dialkyldiamides, resin components, conventional polymers, porous rubbers, fluxing agents, asphaltenes, oils of origin vegetable or mineral and their derivatives, as well as those used to reduce the temperature of production of a mix.

18. Use of a polycondensate according to any one of claims 10 to 16, a formulation according to claim 17, or a bituminous composition according to any one of claims 1 to 8, for the coating of motorable surfaces , waterproofing applications and the preparation of adhesive formulations.

19. A coating comprising a polycondensate according to any of claims 10 to 16, a formulation according to claim 17 or a bituminous composition according to any one of claims 1 to 8 and mineral aggregates.

20. A road surface coated in whole or in part with a bituminous composition according to any one of claims 1 to 8 or with an asphalt mix according to claim 19.