Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
  • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/201—Pre-melted polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08J2409/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2555/00—Characteristics of bituminous mixtures
  • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
  • C08L2555/80—Macromolecular constituents
  • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers

Definitions

• the present invention relates to the technical field of bitumens. More specifically, it relates to bituminous compositions which comprise a combination of elastomer and olefinic polymer adjuvant, in a heat-crosslinked form, having improved aging properties.
• the invention also relates to the processes for preparing such compositions, as well as their uses in the road field and in the industrial field.
• bituminous compositions have already been the subject of numerous studies. In fact, in order to be able to be used as a binder in these various applications, a bitumen must have certain chemical, physical and mechanical properties. It is well known that the properties of pure bitumens can be altered by the addition of polymers. Mention may be made, for example, of the addition of copolymers of aromatic monovinyl and of conjugated diene, such as copolymers of styrene and of butadiene.
• bitumen / polymer compositions are markedly improved when, for their preparation, polymers of aromatic monovinyl hydrocarbon and of conjugated diene are used. , such as the copolymers of styrene and of butadiene, which can be crosslinked using sulfur-based or heat-crosslinkable crosslinking agents, that is to say crosslinkable under the action of heat.
• applications WO 2007/058994, WO 2008/137394 and application WO 2011/013073 in the name of the applicant describe processes for preparing crosslinked bitumen / polymer compositions without a crosslinking agent. In this case, the crosslinking is carried out, only, by heating to a suitable temperature, so that the compositions can be qualified as heat-crosslinked.
• bituminous binders when they are used as a bituminous binder, in the road field or in the industrial field, said bituminous binders are subjected to numerous stresses, in particular to variations in
• bituminous compositions which comprise polymers in heat-crosslinked form did not have a completely satisfactory resistance to aging and to damage due to humidity, to the diffusion of oxygen (oxidation) or to UV radiation, in particular.
• bitumen / polymers as well as new processes for preparing
• bitumen / polymers said compositions exhibiting improved long-term aging properties, while retaining satisfactory mechanical properties, sought after by the addition of the polymers introduced.
• bituminous compositions which exhibit improved aging resistance properties.
• the inventors propose to introduce at least one clay, in bituminous compositions comprising a matrix heat-crosslinked formed from a bitumen / elastomer mixture
• the incorporation of clay particles makes it possible to improve the stability and the resistance to aging of such bituminous compositions, under conditions simulating the aging conditions to which they are subjected, when the latter are used as a bituminous binder, and this without the introduction of clay particles unacceptably affecting the mechanical properties provided by the presence of the elastomer and of the functionalized olefinic polymer adjuvant used to form the bitumen / heat-crosslinked polymer matrix of the bituminous composition.
• the introduction of clay particles which are solid additives, could lead to a significant loss of elasticity and it was by no means obvious that in the case of the usual tests of storage stability, the particles remain in suspension in bitumen.
• cases of the introduction of clay particles into polymeric compositions resulting in the deterioration of the mechanical properties of the materials had been reported.
• the incorporation of the clay made it possible to improve the storage stability of the composition thus obtained, and also to improve the properties of
• bitumen / elastomer mixtures are physical, there is no question of adding a polymer of the SBS type heat-crosslinkable which will crosslink during the hot mixing with the bitumen and even less the addition of an olefinic polymer adjuvant with epoxy groups which during the hot mixing with the bitumen also leads to crosslinking reactions. It was by no means possible, in view of these results of the prior art to predict that the incorporation of clay could have a beneficial effect in the case of bitumen compositions comprising a crosslinked elastomer and an olefinic polymer adjuvant with groups epoxy, as demonstrated in the context of the invention.
• bituminous compositions comprising:
• a heat-crosslinkable elastomer chosen from copolymers with heat-crosslinkable blocks of formula SBS, in which each S independently represents a block based on monovinyl aromatic hydrocarbon monomers, B represents a block based on butadiene monomers, said block B comprising pendant vinyl groups , and in which the S blocks together represent at least 15 mol% of the total number of moles of monomer units of the heat-crosslinkable block copolymer, said heat-crosslinkable block copolymers having a weight average molecular mass ranging from 40,000 to 500 000 g / mol and having a content of pendant vinyl groups greater than or equal to 20% by moles, relative to the total number of moles of monomer units of the heat-crosslinkable block copolymer, and
• olefinic polymer adjuvant or alternatively “olefinic adjuvant” may be used to refer to the olefinic polymer adjuvant functionalized with epoxy groups, and in particular with glycidyl groups.
• the average molecular masses mentioned in the description and the claims can be measured by gel permeation chromatography (GPC) (or SEC for “Size Exclusion Chromatography”.
• GPC is a liquid chromatography method in which polymers are separated according to their hydrodynamic volume, which is then converted by so-called conventional external calibration to weight average molecular mass (Mw) and / or number average molecular mass (Mn).
• Mw weight average molecular mass
• Mn number average molecular mass
• the standards used are generally polystyrene or
• the molecular mass of the polymers measured by GPC is thus a molecular mass in styrene equivalents.
• the detector used is preferably a combination of a UV (ultraviolet) detector and an RI (difference in refractive index) detector.
• matrix formed by heat-crosslinking is meant that the matrix is obtained by crosslinking at least some, or even all, of the crosslinkable functions present on the heat-crosslinkable elastomer SBS and the olefinic polymer adjuvant, these crosslinkable functions corresponding, in particular, to vinyl groups pendent from the block B of the elastomer
• heat-crosslinkable SBS and epoxy groups, and in particular glycidyl, of the olefinic polymer adjuvant will form bridges within the matrix, which may be qualified as a heat-crosslinked matrix. Without being linked by any mechanism of action, these bridges can intervene within the same component of the matrix (the heat-crosslinkable elastomer SBS in particular) or between two components of the matrix (which are the elastomer and the bitumen or olefinic polymer builder and bitumen).
• Crosslinking is called “heat crosslinking” because it only involves heating and in no way a crosslinking agent, leading to so-called chemical crosslinking.
• the mixture subjected to crosslinking is devoid of sulfur or of sulfur compounds, or even of any other crosslinking agent.
• a subject of the invention is also a process for preparing a
• bituminous composition comprising the hot mixture of the bitumen base, of said heat-crosslinkable elastomer SBS and of the olefinic polymer admixture, in particular at a temperature belonging to the range ranging from 150 to 200 ° C, preferably to the range ranging from 160 to 190 ° C and the incorporation of clay particles, before, during or after said mixing.
• the mixture at such a temperature is maintained for at least 1 hour, preferably for a period of 2 to 48 hours, and preferably for a period of 4 to 30 hours.
• the hot mixture is carried out at a sufficient temperature and with sufficient time to cause the heat-crosslinking of the mixture comprising the bitumen base, the said heat-crosslinkable elastomer SBS, the olefinic polymer adjuvant, which then form a heat-crosslinked matrix.
• the introduction of the clay particles is carried out, after said mixing.
• a subject of the invention is also bituminous compositions which are obtained by hot mixing, in particular at a temperature belonging to the range ranging from 150 to 200 ° C, preferably to the range ranging from 160 to 190 ° C:
• Said hot mixing can be carried out in one or more stages, as detailed later in the description. Said hot mixture will cause the heat-crosslinking of the assembly comprising:
• thermoplastic elastomer chosen from copolymers with heat-crosslinkable block of formula S-B-S, also called elastomers
• each S independently represents a block based on monovinyl aromatic hydrocarbon monomers
• B represents a block based on butadiene monomers comprising pendant vinyl groups
• the S blocks together represent at least 15 mol% of the total number of moles of monomer units of the heat-crosslinkable block copolymer
• said heat-crosslinkable block copolymers having a weight average molecular mass ranging from 40,000 to 500,000 g / mol and having a content of pendant vinyl groups greater than or equal to 20% in moles, relative to the total number of moles of monomer units of the heat-crosslinkable block copolymer
• the introduction of the clay particles can be done before mixing the bitumen base, the heat-crosslinkable elastomer SBS and the olefinic polymer additive, intended to constitute the matrix, during their mixing, or after the premixing of the latter, resulting in the heat-crosslinked matrix.
• the clay particles are introduced with stirring accompanied by heating, so as to distribute them in the heat-crosslinked matrix.
• the combined use of clay particles, a heat-crosslinkable elastomer SBS and an olefinic polymer adjuvant in the preparation of a bituminous composition makes it possible to improve the resistance to aging and in particular the resistance to oxidation of the bituminous composition obtained. This improvement is important when the bituminous composition is used in its various applications, in particular as a bituminous binder.
• the introduction of the clay particles makes it possible to improve the resistance to aging, while retaining the benefit of the presence of the SBS heat-crosslinkable elastomer and of the olefinic polymer adjuvant, which are heat-crosslinked within the composition and which provide satisfactory and improved storage resistance and mechanical properties compared with unmodified bitumen.
• bituminous compositions according to the invention find different bituminous compositions according to the invention.
• the invention also relates to:
• bituminous composition according to the invention, to prepare a waterproofing coating, a membrane or an impregnation layer; as well as the methods of preparing such a waterproofing coating, such a membrane or such an impregnation layer;
• bituminous binders comprising a bituminous composition according to the invention
• bituminous composition according to the invention, as a bituminous binder in a bituminous mix comprising a composition
• bituminous according to the invention aggregates, and optionally fillers mineral and / or synthetic; as well as the processes for preparing such a bituminous coating; bituminous mixes comprising a bituminous composition according to the invention, with aggregates, and optionally mineral and / or synthetic fillers;
• bituminous composition according to the invention as a bituminous binder in an asphalt comprising a bituminous composition according to the invention, and mineral and / or synthetic fillers; as well as the processes for preparing such an asphalt; asphalts comprising a bituminous composition according to the invention, with mineral and / or synthetic fillers;
• bituminous composition according to the invention as a bituminous binder in a surface coating, a hot mix, a cold mix, a cold cast mix, a serious emulsion or a wearing course , which comprises a bituminous composition according to the invention of aggregates and / or recycling mills; as well as the methods of preparing such a surface coating, hot coated, cold coated, cold cast coated, of such a severe emulsion or wearing course.
• the invention relates to bitumen compositions modified by adding
• bituminous compositions can include one or more bitumens.
• bitumen (s) present are called “bitumen base” and constitute (s) a majority content of the
• bitumens that are to say represents (s) in general at least 70% by mass, of the total mass of the bituminous composition, and preferably at least 85%, or even at least 90% by mass of the total mass of the bituminous composition.
• bitumens 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 bitumens used are advantageously chosen from bitumens obtained from petroleum refining. crude, in particular bitumens containing asphaltenes or pitches.
• bitumens can be obtained by conventional methods of manufacturing bitumens in a refinery, in particular by direct distillation and / or vacuum distillation of petroleum. These bitumens 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 residues.
• bitumens In the conventional methods of mixing different bitumens, the operation is carried out at temperatures between 100 ° C and 200 ° C, preferably between 140 ° C and 200 ° C, and with stirring for a period of at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
• the temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by standard NF EN 12594.
• Blown bitumens can be manufactured in a blowing unit, by passing a flow of air and / or oxygen. through a bitumen or mixture of starting bitumens. This can be done in the presence of an oxidation catalyst, for example phosphoric acid.
• the blowing is carried out at high temperatures, of the order of 200 to 300 ° C., for relatively long periods, typically between 30 minutes and 2 hours, continuously or in batches.
• the duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
• bitumens that can be used according to the invention, there may also be mentioned recycling bitumens.
• bitumens can be hard grade bitumens (such as the grades
• soft grade such as 160/220 grade
• bitumen base consists of a hard grade bitumen or a mixture of hard grade bitumens, in particular chosen from bitumens of grade 35/50 , 20/30 and 10/20.
• bitumen bases which can be used in the context of the invention preferably 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.
• 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.
• the so-called “needle penetrability” measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C (P25). This
• Penetrability characteristic is expressed in tenths of a millimeter (dmm or 1/10 mm).
• the 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.
• SBS heat-crosslinkable elastomer it may be a single SBS heat-crosslinkable elastomer or a mixture of several SBS heat-crosslinkable elastomers defined in the present description.
• a single SBS heat-crosslinkable elastomer is used, unless it is specified otherwise.
• the heat-crosslinkable elastomer SBS is chosen from copolymers with heat-crosslinkable block of formula S-B-S, in which:
• each S which may be identical or different, independently represents a block based on monovinyl aromatic hydrocarbon monomers
• - B represents a block based on butadiene monomers, said block B comprising pendant vinyl groups
• the S blocks together represent at least 15% by moles of the total number of moles of monomer units of the heat-crosslinkable block copolymer.
• Said heat-crosslinkable block copolymers have an average molecular mass ranging from 40,000 to 500,000 g / mol and have a content of pendant vinyl groups contained in block B, which is greater than or equal to 20 mol%, relative to total number of moles of monomer units of the heat-crosslinkable block copolymer.
• These copolymers may be called, more simply, hereinafter, SBS heat-crosslinkable elastomer.
• the two S blocks of the SBS heat-crosslinkable elastomer are identical.
• butadiene denotes 1,3-butadiene which is a conjugated diene.
• butadiene or more generally a conjugated diene
• the result is a vinyl group (also referred to as a vinyl group) hanging from the backbone of the polymer.
• the pendant vinyl groups of the SBS block copolymer therefore correspond to the polymerization by 1,2 addition of the conjugated diene monomers, and in particular of the majority butadiene monomers, within the block B.
• the units obtained by the polymerization of butadiene according to a mechanism of 1,2-addition or according to a 1,4-addition mechanism have the same molar mass.
• block is meant within the meaning of the invention a polymer chain obtained by the polymerization of one or more monomers of the same chemical nature.
• a block advantageously consists of the repetition of the same monomer.
• the monovinyl aromatic hydrocarbon monomer (s) present in the S blocks of the heat-crosslinkable elastomer SBS are chosen from styrene, Go-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4 -dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or their mixtures.
• the monovinyl hydrocarbon monomer preferred aromatic according to the present invention is styrene, which is used for the constitution of the S blocks as the sole monomer, or as the majority monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely in proportions of not more than 10% in mass, relative to all of the monovinyl aromatic hydrocarbon monomers present in said S block.
• styrene which is used for the constitution of the S blocks as the sole monomer, or as the majority monomer in mixtures with minor proportions of one or more other monomers such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4
• the use of styrene as the sole monomer is particularly preferred in the present invention for the constitution of the S blocks of the heat-crosslinkable elastomer SBS.
• the monovinylaromatic hydrocarbon monomers from which the S blocks of the SBS thermocrosslinkable block copolymers are derived can be, independently, any monovinylaromatic hydrocarbon monomer as described above and are preferably styrene.
• the block B based on butadiene monomers entering into the composition of the block copolymers mentioned SBS is preferably only composed of butadiene monomers, or a mixture of butadiene comprising minor proportions of one or more other dienes structurally related conjugates, and in particular selected from isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene, in particular representing at most 10% by mass, by relative to all the conjugated dienes present in block B.
• the constituent monomers of block B are exclusively butadiene monomers.
• the SBS heat-crosslinkable block elastomer used in the context of the invention has an average molecular mass Mw, ranging from 40,000 to 500,000 g / mol.
• the heat-crosslinkable block elastomer SBS has an average molecular mass Mw, less than or equal to 400,000 g / mol, more preferably less than or equal to 250,000 g / mol, even more preferably less than or equal to 200,000 g / mol and advantageously less than or equal to 150,000 g / mol.
• the SBS block copolymer used in the context of the invention has a weight average molecular mass Mw greater than or equal to 50,000 g / mol, more preferably greater than or equal to 65,000 g / mol, again more preferably greater than or equal to 75,000 g / mol, and advantageously greater than or equal to 100,000 g / mol.
• Mw weight average molecular mass
• the SBS block copolymer has a weight-average molecular mass Mw in any range corresponding to the maximum and minimum values mentioned above, and advantageously in the range ranging from 100,000 to 150,000 g / mol.
• the heat-crosslinkable block copolymer SBS used in the context of the invention has a content of pendant vinyl groups greater than or equal to 20% by moles, relative to the total number of moles of monomer units of the copolymer .
• This vinyl content determined by coupling 13 C NMR (carbon nuclear magnetic resonance) and 1 H NMR (proton nuclear magnetic resonance) spectroscopy techniques, makes it possible to characterize the polymer.
• the SBS block copolymer has a content of pendant vinyl groups in any range corresponding to the maximum and minimum values mentioned above, and advantageously in the range ranging from 28 to 35%.
• the pendant vinyl groups are distributed along block B of the SBS polymer in a statistical manner. This characteristic results directly from the process used for the synthesis of the copolymer.
• the number of moles of monomer units of the S blocks present in the heat-crosslinkable block copolymer SBS together represents at least 15% of the total number of moles of monomer units of the copolymer
• heat-crosslinkable SBS preferably at least 16 mol%.
• the number of moles of monomer units of the S blocks of the SBS polymer represents, together, from 15% to 50% by moles, relative to the total amount of moles of monomer units of the heat-crosslinkable block copolymer SBS, more preferably from 16% to 30% by moles, even more preferably from 16% to 25% by moles, and advantageously from 16% to 20% by moles.
• the number of moles of monomer units of the S blocks of the SBS polymer can be determined by 13 C NMR spectroscopy (Carbon Nuclear Magnetic Resonance).
• the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the heat-crosslinkable block copolymer SBS, determined by 13 C NMR spectroscopy (Carbon Nuclear Magnetic Resonance), is greater than or equal to 25% by mass, more preferably greater than or equal to 28% by mass, even more preferably greater than or equal to 30% by mass, relative to the total mass of the heat-crosslinkable block copolymer of formula SBS.
• the content of monovinyl aromatic hydrocarbon monomer (advantageously styrene) of the heat-crosslinkable block copolymer SBS ranges from 25% to 40% by mass, again more preferably from 28% to 35% by mass, based on the total mass of the block copolymer
• the SBS heat-crosslinkable block elastomers are in an essentially non-hydrogenated form.
• the heat-crosslinkable block copolymer of formula SBS is obtained by coupling two block copolymers of formula SB 'in which the blocks S and B' are chosen to obtain a heat-crosslinkable block copolymer SBS.
• Block B can therefore include a residue of a coupling agent, well known in the field under consideration.
• a difunctional coupling agent mention may be made of dibromoethane, diethyl adipate, divinylbenzene, dimethyldichlorosilane and methyl dichlorosilane.
• gel permeation chromatography is greater than or equal to 50%, more preferably greater than or equal to 75%, even more preferably greater than or equal to 90% and advantageously greater than or equal to 95%.
• a single heat-crosslinkable block copolymer SBS as described in the context of the invention is used, or else a mixture of block copolymers heat-crosslinkable SBS as described in the context of the invention is used, or one or more heat-crosslinkable block copolymer (s) SBS as described in the context of the invention are used in combination with one or more several other heat-crosslinkable elastomers.
• the heat-crosslinked matrix is produced only with one or more, preferably only one, SBS heat-crosslinkable elastomer.
• This last (s) represents (s), preferably, from 0.5 to 10% by mass, in particular from 1 to 6% by mass, and preferably from 1.5 to 4% by mass of the total mass of the bituminous composition.
• the said heat-crosslinkable elastomer (s) is (are) in a heat-crosslinked form, but this does not affect the percentage that it (s) represents ( nt) within the composition.
• the percentages, before and after heat treatment, and therefore crosslinking, of the various components used for the preparation of the bituminous composition are identical to the percentages that they ultimately represent within the bituminous composition in a form. heat-crosslinked.
• the percentages from 0.5 to 10% by weight, in particular from 1 to 6% by mass, and preferably from 1.5 to 4% by mass given relative to the total mass of the bituminous composition, correspond to the total amount of heat-crosslinkable elastomers used (SBS + other heat-crosslinkable elastomer (s) ( s)).
• the SBS heat-crosslinkable elastomer represents at least 50%, preferably at least 70% by weight, and preferably at least. less 90% of the total quantity of heat-crosslinkable elastomers used (SBS + other elastomer (s)
• heat-crosslinkable elastomers one can, for example, cite the heat-crosslinkable elastomers described in application WO 2017/046523.
• the mixture represent at least 80% by mass of the total amount of heat-crosslinkable elastomers, preferably at least 90% and preferably at least 95% of the total amount of heat-crosslinkable elastomers present, if a mixture of heat-crosslinkable elastomers is used to form the heat-crosslinked matrix of the bituminous compositions according to the invention.
• the mixture it is possible for the mixture to contain a portion of S-B ′ used during the manufacture of the heat-crosslinkable elastomer SBS by coupling, as explained previously.
• olefinic polymer adjuvant functionalized with epoxy groups when it comes to olefinic polymer adjuvant functionalized with epoxy groups, it may be of a single olefinic polymer adjuvant functionalized with epoxy groups or of a mixture of several olefinic polymer adjuvants defined in the present description.
• a single olefinic polymer adjuvant is used, unless it is specified otherwise.
• the present invention uses an olefinic polymer adjuvant
• the olefinic polymer adjuvant carries several epoxy groups.
• Said epoxy groups present on the polymer will preferably all be identical, although it is not excluded that the olefinic polymer adjuvant may carry different epoxy groups.
• said olefinic polymer adjuvant is functionalized with glycidyl groups, as epoxy group.
• the olefinic polymer adjuvant carries several glycidyl groups, said glycidyl groups being identical.
• bituminous compositions according to the invention advantageously comprise from 0.05 to 2.5% by mass, in particular from 0.15 to 2% by mass, and preferably from 0.2 to 1% by mass , of olefinic polymer additive, relative to the total mass of the bituminous composition.
• said olefinic polymer adjuvant is in a heat-crosslinked form, but this does not affect the percentage which it represents in the composition.
• the percentages, before and after heat treatment, and therefore crosslinking, of the various components used for the preparation of the bituminous composition are identical to the percentages which they ultimately represent within the bituminous composition.
• the olefinic polymer adjuvant is chosen from (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer C terpolymers, and mixtures thereof.
• Monomer A is chosen from vinyl acetate and C1 to C6 alkyl acrylates and methacrylates and monomer C is chosen from glycidyl acrylate and glycidyl methacrylate and (d) mixtures thereof.
• the olefinic polymer adjuvant is preferably chosen from:
• 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;
• the olefinic polymer adjuvant is chosen from
• the olefinic polymer adjuvant is chosen from random or block terpolymers, preferably random, of ethylene, of a monomer A chosen from vinyl acetate and C1 to C1 alkyl acrylates or methacrylates.
• terpolymers comprising from 0.5% to 40% by mass, preferably from 10% to 30% by mass 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 C, the remainder being formed from units derived from ethylene.
• the olefinic polymer adjuvant is chosen from
• random terpolymers of ethylene of a monomer A chosen from C1 to C6 alkyl acrylates or methacrylates and of a C monomer chosen from acrylate of glycidyl and glycidyl methacrylate, said terpolymers comprising from 0.5% to 40% by mass, preferably from 10% to 30% by mass of units derived from monomer A and, from 0.5% to 15% by mass , preferably from 2.5% to 15% by weight of units derived from monomer C, the remainder being formed from units derived from ethylene.
• the olefinic polymer adjuvant is chosen from the random terpolymers of ethylene, of a monomer A chosen from C1 to C3 alkyl acrylates or methacrylates and of a C monomer chosen from glycidyl acrylate and glycidyl methacrylate, said terpolymers comprising from 0.5% to 40% by mass, preferably from 10% to 30% by mass of units derived from monomer A and, from 0.5% to 15 % by mass, preferably from 2.5% to 15% by mass of units derived from monomer C, the remainder being formed from units derived from ethylene.
• the monomer A is chosen from ethyl acrylate and methacrylate.
• the number-average molecular mass (Mn) of the olefinic polymer adjuvant used belongs to the range ranging from 5,000 to 50,000 g / mol, more preferably in the range ranging from 10,000 to 40,000 g / mol, and even more preferably in the range going from 25,000 to 40,000 g / mol.
• Mn can be determined by gel permeation chromatography with a polystyrene standard.
• the olefinic polymer adjuvant used belongs to the range going from 10,000 to 250,000 g / mol, more preferably to the range ranging from 50,000 to 200,000 g / mol, and even more preferably to the range ranging from 10,000 to 150 000 g / mol.
• Mw can be determined by gel permeation chromatography with a polystyrene standard, as mentioned above.
• bituminous compositions whatever the embodiment concerned, comprise clay particles.
• these clay particles can be introduced at different stages, as will be detailed later.
• the clay used in the context of the invention can be chosen from
• bentonite and montmorillonite As is known, bentonite contains montmorillonite (generally around 90%) and other components. Montmorillonite corresponds to a bentonite which has been purified.
• the clay used can be organically modified or not modified.
• the clay inorganically, in the latter case the clay can be qualified as inorganic.
• bituminous compositions according to the invention can comprise a single type of clay or a mixture of different clays.
• the processes according to the invention can therefore use a single type of clay or a mixture of different clays.
• the clay particles have an average size d 5o less than or equal to 100 mm, preferably less than or equal to 10 ⁇ m, than the clay may or may not be organically modified.
• Such clay particles are conventionally called nanoclays.
• the mean size d 5o is defined as follows: 50% by mass of the population of particles has a size less than d 50 , and can be obtained by analysis under dry laser diffraction.
• the clays are, in general, of platelet form with a thickness much less than the dimensions in the plane of the platelet.
• the clay particles present in the bituminous composition are particles of organically modified clay.
• Such nanoparticles are commercially available, in particular under the Dellite® references marketed by Laviosa (Italy), under the Cloisite® references marketed by BYK (Germany) and under the Nanomer® references marketed by Nanocor (USA). They can also be obtained by exchange of cations between sodium or calcium cations initially present in the clay particles and an organic cation, in particular of the type quaternary ammonium, present in organic salts, of the chloride type for example.
• the organically modified clay particles exhibit an onset temperature of degradation in air greater than or equal to 175 ° C, as described in application FR 17 62433.
• the temperature at the start of degradation of the organically modified clay particles is, in particular, measured in the context of the invention, using a thermogravimetric analyzer, by placing the organically modified clay particles under a flow rate of 60 ml / min of air containing 21% oxygen. The temperature is increased by 10 ° C / min.
• the value of the temperature of the start of degradation is obtained by plotting the derivative of the loss of mass as a function of the temperature (% / ° C), as illustrated in Figure 1.
• the clay particles used in the context of the invention can be organically modified by various organic modifiers.
• the organic modifier used does not include an OH function and / or the organic modifier used does not include an aromatic group.
• organic modifiers can be chosen from:
• cations comprising at least one hydrogenated soot group (in English "hydrogenated tallow"), preferably comprising two hydrogenated soot groups, and in particular quaternary ammonium cations, and in particular those comprising an OH function, such as methyl di (2) -hydroxyethyl) (hydrogenated soot) ammonium of formula:
• the clay particles whether or not the clay is organically modified, have, before mixing with the other components of the bituminous compositions, a distance d (001) less than or equal to 5 nm, preferably less than or equal to 4 nm. This distance corresponds to the distance separating the sheets constituting the clay particles.
• the organically modified clay particles will exhibit, before mixing with the other components of the bituminous compositions, a distance d (001) of at least 2.6 nm, preferably at least 3.2 nm, or even d.
• the distance d (001) from the clay before adding the organic modifier and the nature of the organic modifier influences the degradation temperature of the organically modified clay.
• a distance d (001) of at least 2.6 nm, preferably at least 3.2 nm, or even at least 3.5 nm for the organically modified clay particles, before mixing with the other components of bituminous compositions is particularly suitable for clays modified with a cation comprising at least one hydrogenated soot group as described above.
• a distance d (001) before mixing with the other components of the bituminous compositions which is lower, in particular in the range from from 2 to 5 nm, may lead to a degradation T of less than 175 ° C.
• d (001) before incorporation into the bituminous composition of at least 3.2 nm, preferably at least 3.5 nm, in particular in a range ranging from 3.2 to 5 nm or ranging from 3 , 5 to 5 nm or ranging from 3.2 to 4 nm or ranging from 3.5 to 4 nm,
• the clay particles are organically modified with methyl di (hydrogenated soot) ammonium, or preferably with dimethyl di (hydrogenated soot) ammonium.
• organically modified clay particles with an onset temperature of degradation in air greater than or equal to 175 ° C which can be used within the framework of the invention
• the clay particles are arranged in [0070] according to particular embodiments.
• organically modified materials used comprise 20 to 50 wt%, preferably 30 to 50 wt% organic modifier, based on the total mass of the organically modified clay particles.
• the bituminous compositions according to the invention generally comprise from 0.1 to 20% by mass, in particular from 0.5 to 10% by mass, and in particular from 1 to 5% by mass, and more preferably from 2 to 4% by mass, of clay particles, relative to the total mass of the bituminous composition, whether or not the clay is organically modified. In the event that the clays are
• the clay content may be lower, in particular from 0.5 to 6% by mass, in particular from 1 to 4% by weight. mass, and in particular from 1 to 3% by mass, of clay particles, relative to the total mass of the bituminous composition.
• bituminous compositions according to the invention can also comprise one or more non-crosslinkable plastomers and / or elastomers different from those previously described and / or one or more other additives.
• bituminous composition and the mixtures used for its preparation may, in fact, comprise one or more plastomers and / or elastomers, in addition to the heat-crosslinkable elastomer or elastomer previously described and the functionalized olefinic polymer adjuvant.
• composition according to the invention may contain other ingredients.
• elastomers for bitumen such as copolymers S1-B'l-B'2 (styrene-butadiene-butadiene block copolymer in which the two butadiene blocks B'1 and B'2 have a different vinyl content), SIS (styrene -isoprene-styrene), SBS * (star-shaped styrene-butadiene-styrene block copolymer), SBR (styrene butadiene rubber), EPDM (modified ethylene propylene diene), polychloroprene, polynorbornene, natural rubber, recycled rubber, polybutene,
• copolymers S1-B'l-B'2 styrene-butadiene-butadiene block copolymer in which the two butadiene blocks B'1 and B'2 have a different vinyl content
• SIS styrene -isoprene-st
• polyisobutylene SEBS (copolymer of styrene, ethylene, butylene and styrene).
• bituminous composition according to the invention may also contain, in addition, one or more plastomers chosen from the category of Known bitumen plastomers such as polyethylenes PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene-vinyl acetate copolymer), EMA (polyethylene-methyl acrylate copolymer), olefin and olefin copolymers unsaturated carboxylic esters, EBA
• polyethylene-butyl acrylate copolymer copolymers of ethylene and esters of acrylic, methacrylic or maleic anhydride, ethylene-propylene copolymers, ABS (acrylonitrile-butadiene-styrene).
• bituminous composition according to the invention comprises at least one plastomer and / or an elastomer (not heat-crosslinkable) as defined above
• the latter or these (plastomer (s) and / or elastomer (s) non-heat-crosslinkable (s) present) represent (s) at most 30% by mass of the total mass of heat-crosslinkable elastomer SBS, preferably at most 20% by mass, even more preferably at most 10% by mass .
• bituminous compositions according to the invention can be any bituminous compositions according to the invention.
• additives chosen from:
• tackifier dopes and surfactants are generally chosen from derivatives of alkylamines, derivatives of alkylpolyamines, derivatives of alkylamidopolyamines, derivatives of alkylamidopolyamines and derivatives of quaternary ammonium salts, taken alone or as a mixture.
• the quantity of tackifier (s) and / or surfactant (s) present in the bituminous compositions according to the invention is, for example, between 0.2% and 2% in mass, preferably between 0.5% and 1% by mass, relative to the total mass of said bituminous composition.
• waxes of animal, vegetable or hydrocarbon origin in particular long chain hydrocarbon waxes, for example polyethylene waxes or paraffins, possibly oxidized.
• Amide waxes such as ethylene bis-stearamide can also be added.
• paraffins having chain lengths of 30 to 120 carbon atoms (C 30 to C 120 ).
• Paraffins are chosen from polyalkylenes.
• the paraffins are polymethylene paraffins and polyethylene paraffins. These paraffins may be of petroleum origin or come from the chemical industry.
• the paraffins are synthetic paraffins obtained from the conversion of biomass and / or natural gas.
• paraffins can also contain a large proportion of so-called “normal” paraffins, that is to say straight chain, unbranched paraffins (saturated hydrocarbons).
• the paraffins can comprise from 50 to 100% normal paraffins and from 0 to 50% isoparaffins and / or branched paraffins.
• the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins and / or branched paraffins.
• the paraffins comprise from 50 to 100% normal paraffins and from 0 to 50% isoparaffins.
• the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.
• the paraffins are polymethylene paraffins. More particularly, paraffins are synthetic paraffins of
• polymethylene in particular paraffins resulting from the conversion of synthesis gas by 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.
• the paraffins are Fischer-Tropsch polymethylene paraffins sold by Sasol, in particular under the trademark Sasobit®.
• oils based on animal and / or vegetable fats or hydrocarbon oils of petroleum origin may be in the form of free fatty acids, triglycerides, diglycerides or monoglycerides, in esterified form, for example in the form of methyl ester.
• resins of plant origin such as rosins.
• anti-foam additives in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides obtained from vegetable or animal oils.
• amines chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines; imidazolines.
• lubricating additives or anti-wear agents 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- and carboxylic acid derivatives. polycyclic.
• antioxidants for example of hindered phenolic type or amine type of alkylated paraphenylene diamine type.
• xii) 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.
• xiii) acids such as polyphosphoric acid or diacids, in particular fatty diacids.
• Such additives when they are present, are used in amounts suitable for those skilled in the art, depending on the nature of the additive, depending on the bitumen base and the expected properties.
• composition When it comprises one or more of these additives, the composition:
• bituminous material according to the invention comprises, in general, from 0.1% to 10% by mass, preferably from 0.5% to 5% by mass, more preferably from 0.5% to 2.5% by mass of additive (s) relative to the total mass of the bituminous composition.
• bituminous compositions also called bitumen comoositions. according to the invention - preferred embodiments
• bituminous compositions according to the invention comprise one or more other components, in particular chosen from those conventionally used in bituminous compositions as previously described in the previous paragraph, preferably, the bitumen base, the heat-crosslinkable elastomer SBS, the olefinic polymer admixture and the clay particles (whether or not the clay is organically modified) represent at least 90% by mass, preferably at least 95% by mass, or even 100% by mass of the total mass of the bituminous composition.
• the heat-crosslinkable elastomer SBS and the olefinic polymer adjuvant are called, in the same way as in the mixture before heat-crosslinking, while the latter are in heat-crosslinked form in the matrix which they form with the bitumen base, in the bituminous compositions according to the invention.
• the clay particles are dispersed in the heat-crosslinked matrix which is composed, in particular, of the bitumen base, of the heat-crosslinkable elastomer SBS and of the olefinic polymer adjuvant.
• the clay particles are distributed in the matrix making up the
• bituminous compositions according to the invention consisting of a mixture of bitumen, of the heat-crosslinkable elastomer SBS and of the olefinic adjuvant described above, which have been subjected to a heating operation resulting in the crosslinking of at least one part, or even all of the crosslinkable functions present on the heat-crosslinkable elastomer SBS and the olefinic adjuvant.
• the crosslinking of said functions can take place by creating crosslinking bridges, in particular within the heat-crosslinkable elastomer SBS, between the heat-crosslinkable elastomer SBS and the bitumen, and / or between the olefin admixture and the bitumen, without being linked by some mechanism of action.
• crosslinking bridges in particular within the heat-crosslinkable elastomer SBS, between the heat-crosslinkable elastomer SBS and the bitumen, and / or between the olefin admixture and the bitumen, without being linked by some mechanism of action.
• the presence of the crosslinks does not affect the hot-meltable nature of the bituminous composition thus obtained, but its mechanical properties and, in particular, its tensile characteristics are greatly improved and remain satisfactory despite the incorporation of clay particles.
• bituminous compositions obtained according to the processes described in the context of the invention is thus called heat-crosslinked.
• the concept of heat-crosslinked means that the crosslinking is obtained only by heating, that is to say without the presence of a crosslinking agent.
• Crosslinking is achieved without the use of sulfur or a sulfur crosslinking agent.
• the temperature and the time required to obtain crosslinking in the matrix are adjusted by those skilled in the art, depending, in particular, on the nature of the SBS heat-crosslinkable elastomer and of the olefinic adjuvant used and their quantity.
• the crosslinking of the matrix can be obtained by mixing the bitumen base, the elastomer
• heat-crosslinkable SBS and the olefinic polymer adjuvant at a temperature belonging to the range from 150 to 200 ° C, preferably to the range from 160 to 190 ° C, for at least 1 hour, in particular for a period of 2 to 45 hours, preferably 4 to 30 hours.
• the clay particles can be completely exfoliated. In this case, it is not possible to measure a distance d (001) on the obtained X-ray diffraction spectrum.
• the matrix will advantageously be interposed in the clay particles.
• Such a distribution is in particular illustrated in the publication by A. Zare-Shabadi et al., Construction and Building Materials 2010, 24, 1239-1244, FIG. 1.
• the clay particles have, in the
• bituminous composition according to the invention, a distance d (001) in the range going from 3.6 to 5 nm, preferably in the range going from 4 to 5 nm, preferably in the range going from 4 to 4.7 nm. This distance is greater than that observed before incorporation of the clay particles in the bituminous composition.
• the incorporation of the clay particles in combination with the heat-crosslinkable elastomer SBS and the olefinic polymer adjuvant, both subjected to heat-crosslinking in a bitumen base and thus forming a heat-crosslinked matrix makes it possible to improve the resistance to aging of the bituminous compositions obtained, and in particular the resistance to oxidation.
• the examples show, in particular, that the improvement in the resistance to aging of the bitumen compositions thus obtained is not accompanied by a marked degradation of the mechanical properties of said compositions resulting from the matrix.
• bituminous compositions according to the invention can be obtained with any combinations of bitumen base / SBS heat-crosslinkable elastomer / olefinic polymer adjuvant / clay particles as described in the present description.
• bitumen base / SBS heat-crosslinkable elastomer / olefinic polymer adjuvant / clay particles as described in the present description.
• an elastomer, an olefinic polymer adjuvant and clay particles corresponding to those specifically described or to those mentioned as preferred in the corresponding paragraphs of the present description are preferably used.
• compositions according to the invention comprise the following combinations:
• an olefinic polymer adjuvant chosen from random terpolymers of ethylene, of a monomer A chosen from C1 to C3 alkyl acrylates or methacrylates and of a C monomer chosen from glycidyl acrylate and glycidyl methacrylate , said terpolymers comprising from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and, from 0.5% to 15 % by mass, preferably from 2.5% to 15% by mass of units resulting from monomer C, the remainder being formed from units resulting from ethylene, as olefinic polymer adjuvant, - organically modified clay particles exhibiting a temperature at the start of degradation in air greater than or equal to 175 ° C as defined in the context of the invention, as clay particles,
• the crosslinkable elastomer SBS / olefinic polymer adjuvant mass ratio is advantageously from 15 to 2, preferably from 12 to 5. These mass ratios apply equally to the mixtures used for the constitution of the matrix of bituminous compositions according to the invention, therefore before heat-crosslinking, as for bituminous compositions, therefore after heat-crosslinking.
• the crosslinkable elastomer SBS / clay particles mass ratio is advantageously from 0.2 to 5, preferably from 0, 5 to 3.
• these mass ratios are valid as much for the mixtures used for constituting the matrix of the bituminous compositions according to the invention, therefore before heat-crosslinking, as for the bituminous compositions, therefore after the heat-crosslinking.
• bituminous compositions of the invention can be prepared by any method known to those skilled in the art. Typically, these methods include mixing the components and heating the mixture.
• the bitumen can be heated before mixing, in particular to a temperature belonging to the range going from 150 to 200 ° C, preferably to the range going from 160 to 190 ° C.
• the bitumen is heated before mixing, and the other component (s) are added to the bitumen without having been previously heated.
• bituminous composition according to the invention is prepared by hot mixing, in one or more steps: - the bitumen base,
• bituminous composition according to the invention is prepared by mixing, in one or more steps:
• bitumen and in general at least 70% by mass, preferably at least 85%, and preferably at least 90% by mass of bitumen,
• - comprises from 0.1 to 20% by mass, in particular from 1 to 5% by mass, and more preferably from 2 to 4% by mass, of clay particles of clay particles, as defined in the context of the invention,
• the ranges mentioned first for each of the constituents will be used in combination, or the ranges mentioned second for each of the constituents will be used in combination, or the ranges mentioned third for each of the constituents will be used in combination.
• the methods according to the invention preferably use an SBS heat-crosslinkable elastomer, an olefinic polymer adjuvant and clay particles presented as preferred in the context of the invention.
• use will be made, advantageously, of organically modified clay particles having an onset temperature of degradation in air greater than or equal to 175 ° C.
• an SBS heat-crosslinkable elastomer in which styrene is the only monomer present in the S blocks and butadiene is the only monomer present in the B block and an olefinic polymer adjuvant chosen from random terpolymers of ethylene, of a monomer A chosen from among alkyl acrylates or methacrylates in C1 to C3 and a C monomer chosen from glycidyl acrylate and glycidyl methacrylate, said terpolymers comprising from 0.5% to 40% by mass, preferably from 5 to 35% by mass, 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 C, the remainder being formed of units from ethylene.
• the heat-crosslinkable elastomer SBS and the olefinic polymer adjuvant are at least partially crosslinked, within bituminous compositions which comprise a matrix obtained from a mixture of one or more bases bitumens, one or more SBS heat-crosslinkable elastomers and one or more functionalized olefinic polymer adjuvants, said mixture being subjected to a heating step leading to the crosslinking of at least part, or even all of the crosslinkable functions present on the heat-crosslinkable elastomer and the functionalized olefinic polymer adjuvant.
• the process for preparing bituminous compositions implements a thermal crosslinking step. No chemical crosslinking agent is used. Those skilled in the art are able to adapt the temperature and the mixing time used in the process according to the invention, to obtain such
• the method according to the invention does not include the use and, therefore the incorporation during temperature mixing operations, of sulfur, a sulfur crosslinking agent, or even any other crosslinking agent which could lead to the chemical crosslinking of the crosslinkable functions present on the heat-crosslinkable elastomer SBS and the olefinic polymer adjuvant.
• the incorporation of the heat-crosslinkable elastomer SBS and of the olefinic polymer adjuvant within the composition leading to a homogeneous mixture with the bitumen base can be carried out, before or after the incorporation of the clay particles. Additionally, the olefinic polymer builder can be incorporated into the bitumen before or after the SBS heat-crosslinkable elastomer.
• thermocrosslinkable elastomer SBS the thermocrosslinkable elastomer SBS, the olefinic polymer admixture and the bitumen base, are mixed and subjected to a heating operation leading to the thermocrosslinking and to obtaining a heatcrosslinked matrix, before the introduction of the clay particles.
• heat-crosslinkable SBS and the olefinic polymer builder is carried out at temperatures ranging from 150 to 200 ° C, preferably ranging from 160 to 190 ° C.
• Such a mixture is carried out with stirring, in particular, for a period of at least 1 hour, preferably for a period of 2 to 48 hours, and preferably for a period of 4 to 30 hours.
• Said mixture leading to obtaining the heat-crosslinked matrix can be implemented by means of stirring producing a high shear or stirring producing a low
• heat-crosslinked is carried out with stirring at 1000 to 10,000 rpm, preferably from 2000 to 5000 rpm, and preferably from 2500 to 4000 rpm.
• Stirring is carried out so as to facilitate the dispersion and good distribution of the clay in the heat-crosslinked matrix.
• Those skilled in the art will adjust the time and power of the agitation, to achieve exfoliation, or preferably intercalation with the matrix, as desired.
• Said mixture leading to obtaining the heat-crosslinked matrix may comprise successive sequences with different stirring modes, for example the process of the invention may comprise, for obtaining the heat-crosslinked matrix, at least two successive agitation sequences, a first sequence producing high shear agitation followed by a second sequence producing low shear agitation, preferably ranging from 400 rpm to 1000 rpm.
• the clay particles are
• this incorporation is also carried out by hot mixing, at an identical temperature, or, preferably, at a temperature lower than that used for the heat-crosslinking.
• a temperature less than or equal to 180 ° C, preferably less than or equal to 170 ° C is used.
• the introduction of the clay particles and the mixing of the clay particles and the various constituents of the matrix is carried out at temperatures ranging from 100 to 180 ° C, preferably ranging from 120 to 180 ° C, and preferably ranging from 140 to 170 ° C.
• Such lower temperatures are particularly suitable when the organically modified clay particles have an onset temperature of degradation in air greater than or equal to 175 ° C.
• the mixing can be carried out by means of agitation producing a high shear or an agitation producing a low shear. Stirring at high shear, carried out by passing through a high shear mill, makes it possible to facilitate good dispersion and good distribution of clay particles within the matrix.
• the mixture with the clay particles is carried out with stirring at 1000 to 10,000 rpm, preferably from 2000 to 5000 rpm, and
• bituminous composition The introduction of the various components of the bituminous composition, the mixing and the heating are carried out in a suitable reactor.
• additives When other additives are present in the composition, they can be introduced at any stage.
• bituminous compositions obtained according to the invention can be used as a bituminous binder.
• the bituminous binder or bituminous composition according to the invention can in turn be used to prepare an association with aggregates, in particular road.
• 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.
• bituminous coating is meant a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers.
• the bituminous coating comprises a bituminous binder as described in the context of the invention, and optionally mineral and / or synthetic fillers, of 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.
• a subject of the invention is also a process for preparing a bituminous mix comprising the hot mixing of a composition
• bituminous according to the invention with aggregates, and optionally mineral and / or synthetic fillers.
• bituminous binder according to the invention can advantageously be used to prepare a surface coating, a hot mix, a cold mix, a cold cast mix or a serious emulsion.
• the invention also relates to asphalts as a material for making and covering sidewalks.
• asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers.
• An asphalt comprises a composition
• 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.
• asphalts are not compacted with a roller during their placement.
• a subject of the invention is also a process for preparing an asphalt comprising the hot mixing of a bituminous composition according to the invention, with mineral and / or synthetic fillers.
• Another aspect of the invention relates to the use of a bituminous composition in various industrial applications, in particular for preparing a waterproofing coating, a membrane or an impregnation layer.
• bituminous compositions mention may be made of the manufacture of waterproofing membranes, anti-noise membranes, insulation membranes, surface coverings, carpet tiles, impregnation layers.
• Figure 1 shows the thermogravimetric analysis curve - ATG obtained for Dellite® 67G clay.
• bituminous compositions are evaluated by:
• the sample of clay particles was placed under an air flow containing 21% v / v oxygen (02) of 60 mL / min.
• the temperature at the start of degradation was obtained by a thermogravimetric analysis (TGA) measurement with a temperature rise ramp of 10 ° C./min.
• the value of the temperature at the start of degradation was obtained by plotting the derivative of the loss of mass as a function of the temperature (% / ° C).
• the temperature at the start of degradation was measured on clays which had previously been dried at 110 ° C. for 1 hour (to eliminate any presence of humidity).
• ethyl / glycidyl methacrylate in proportions by mass, determined by proton nuclear magnetic resonance, respectively 74/16/10 and having an MFR melt index (190 ° C / 2.16 kg) cè 8g / 10min, calculated according to standard ASTM D1238-IS01 133.
• This polymer is commercially available under the name Elvaloy® 5170P from the company Dupont.
• styrene / butadiene / styrene comprising 30.5% by mass of styrene and 69.5% by mass of butadiene.
• the content of pendant vinyl groups resulting from the 1,2-addition polymerization of butadiene is 27.8% by mass relative to the total mass of copolymer.
• the copolymer has a weight average molecular weight (Mw) of 142,500 Daltons and a polydispersity index Ip of 1.09. This copolymer is commercially available from the company
• the pure bitumen is heated beforehand to 160 ° C in an oven, then transferred to a 3L reactor in which it is heated for 1 hour at 180 ° C. [0132]
• the elastomer and the olefinic polymer additive are then added and the mixture ground for 30 min at 6000 rev / min, still at 180 ° C., using a high shear rotor-stator (Silverson).
• the reactor is then placed under mechanical stirring at 400 rpm for 5.30 hours at 180 ° C., then the stirring is reduced to 200 rpm for 18 hours.
• compositions according to the invention comprising an elastomer / olefinic polymer admixture mixture and wing particles
• the pure bitumen is heated to 150 ° C., then the clay is added and mixed with the bitumen by high shear grinding (Silverson) at 3600 rpm, while maintaining the same temperature for 30 min.
• Table 2 summarizes the amounts of the various constituents used for the preparation of bituminous compositions.
• the amounts given in Table 2 are% by mass, relative to the total mass of the components introduced, which corresponds to the% by mass of the corresponding constituents, but in a crosslinked form for the elastomer and the olefinic adjuvant, present in the bituminous compositions obtained.
• the clay has the effect of limiting the aging of a bituminous composition, and this in a fairly comparable manner whether the composition comprises the bitumen alone or a crosslinked matrix formed from a mixture comprising the elastomer / olefinic polymer adjuvant combination.

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