EP3841164A1 - Composition bitumineuse thermoreversible - Google Patents
Composition bitumineuse thermoreversibleInfo
- Publication number
- EP3841164A1 EP3841164A1 EP19782650.6A EP19782650A EP3841164A1 EP 3841164 A1 EP3841164 A1 EP 3841164A1 EP 19782650 A EP19782650 A EP 19782650A EP 3841164 A1 EP3841164 A1 EP 3841164A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bituminous
- bituminous composition
- bitumen
- carbon atoms
- chosen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
-
- 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
-
- 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
- C08L2555/60—Organic non-macromolecular ingredients, e.g. oil, fat, wax or natural dye
Definitions
- the present invention belongs to the field of bitumens.
- a first aspect of the invention relates to new bituminous compositions comprising new molecules. These bituminous compositions are hard and have a good consistency at use temperatures and a viscosity similar to that of conventional bitumens of the same grade at application temperatures.
- the invention relates to said solid compositions and in divided form at room temperature.
- the invention also relates to a process for the preparation of these bituminous compositions, in particular when they are solid and in divided form at room temperature, and their use in the fields of road applications, in particular in the manufacture of road binders, mixes and pavements in general, and in the fields of industrial applications.
- the present invention also relates to a process for the manufacture of mixes from bituminous compositions according to the invention, as well as a method of transport and / or storage and / or handling of said bituminous compositions, in particular at high ambient temperature.
- the invention also relates to new molecules which can be used in particular in the formulation of bituminous compositions, preferably in the form of solid bituminous compositions and in divided form at room temperature.
- Bitumen or bituminous binder is the main hydrocarbon binder used in the field of road construction or civil engineering. To be able to be used as a binder in these different applications, the bitumen must have certain physico-chemical and mechanical properties. It must in particular be sufficiently hard and have a good consistency at the temperatures of use to avoid, for example, the formation of ruts caused by traffic. Bitumen must also be elastic to resist deformations imposed by traffic and / or temperature changes, phenomena which lead to cracking of asphalt or tearing of surface aggregates. Finally, the bitumen must be sufficiently fluid at the lowest possible application temperatures to allow for example a good coating of aggregates and the installation of the asphalt on the road. The use of a bituminous binder therefore requires combining both the hardness, the consistency and even the elasticity of the bitumen at use temperatures and a low viscosity at application temperatures.
- bitumen alone is not generally elastic enough
- polymers are added to the bitumen which can be optionally crosslinked.
- These crosslinked polymers provide bituminous compositions with markedly improved elastic properties.
- cross-linking is generally irreversible: once cross-linking has been carried out, it is not possible to return to the initial state existing before the cross-linking reaction.
- the crosslinked bituminous compositions thus have good elastic properties, but the viscosity of these is very high.
- One of the drawbacks associated with this high viscosity is the need to heat the crosslinked bitumen to an application temperature higher than that of an uncrosslinked bitumen, which increases energy costs and requires the use of additional protections for operators. .
- bitumen is stored and transported hot, in bulk, in tankers or by ships at high temperatures in the range of 120 ° C to 180 ° C.
- the storage and transport of hot bitumen has certain drawbacks.
- the transport of hot bitumen in liquid form is considered dangerous and it is highly regulated from a regulatory point of view. This mode of transport does not present any particular difficulties when the transport equipment and infrastructure are in good condition. Otherwise, it can become problematic: if the tanker is not sufficiently insulated, the viscosity of the bitumen may increase during a journey that is too long. Bitumen delivery distances are therefore limited.
- keeping bitumen at high temperatures in tanks or in tankers consumes energy.
- keeping the bitumen at high temperatures for a long time can affect the properties of the bitumen and thus change the final performance of the mix.
- thermoreversible crosslinked bituminous compositions based on the use of organogelling additives.
- the thermoreversible crosslinked bituminous compositions thus obtained are hard at use temperatures and have a reduced viscosity at application temperatures.
- bitumen granules comprising a chemical additive. These bitumen granules allow the transport and / or storage and / or handling of the bitumen at room temperature without it leaking, as well as the reduction of their adhesion and agglomeration between them.
- bituminous composition comprising a bitumen and an organogelling molecule which is a dicarboxylic acid comprising between 6 and 12 carbon atoms.
- bituminous composition comprising at least one bitumen and at least one molecule of general formula (I).
- bituminous compositions thus developed have the advantage that they have good hardness and good consistency at temperatures of use, satisfactory mechanical properties, in particular good elasticity, and that they exhibit, at application temperatures, a viscosity similar to that of conventional bitumens of the same grade.
- bituminous compositions according to the invention have the advantage that they are solid at room temperature and allow the shaping of the bitumen in divided form, in particular in the form of granules or breads.
- bituminous compositions which are solid at room temperature and in divided form also make it possible to avoid, reduce and / or delay the adhesion and agglomeration of granules or breads during their transport and / or storage and / or handling at room temperature, in particular at high room temperature, for long periods, compared to bitumen-based materials prior art.
- These bituminous compositions which are solid at room temperature and in divided form retain their properties over time.
- the objective of the present invention is to propose new bituminous compositions comprising the molecules of general formula (I) according to the invention.
- Another objective of the invention is to provide bituminous compositions having good physicochemical and mechanical properties at use temperatures, in particular in terms of hardness, consistency, or even elasticity, but also having at temperatures of application, a reduced viscosity, even equivalent to that of a non-additive bitumen.
- Another objective of the invention is to propose a simple process for the preparation of bituminous compositions comprising said molecules of formula (I).
- Another objective of the invention is to provide bituminous compositions which are solid at room temperature and which allow bitumen to be shaped in divided form, in particular in the form of granules or breads.
- Another objective of the invention is to provide bituminous compositions which are solid at room temperature and in divided form having good hardness and good consistency at use temperatures without degrading the mechanical properties of the bitumen.
- the aim is to obtain compositions having a viscosity similar to that of standard bitumens of the same grade at application temperatures.
- Another objective of the invention is to provide bituminous compositions which are solid at room temperature and in divided form, making it possible to avoid and reduce and / or delay the adhesion and agglomeration of the granules or breads during their transport. and / or storage and / or handling at ambient temperature, in particular at high ambient temperature, over long periods while retaining their properties over time.
- Another objective of the invention is to propose new molecules capable in particular of forming a thermoreversible network in bituminous compositions.
- the invention relates to a bituminous composition
- a bituminous composition comprising at least one bitumen and at least one molecule of general formula (I):
- Rc represents a hydrocarbon chain comprising from 4 to 26 carbon atoms and optionally comprising one or more heteroatoms
- R A and R b identical or different, represent a hydrocarbon group comprising from 4 to 200 carbon atoms, and optionally comprising one or more heteroatoms,
- - X and X ’ identical or different, represent a chemical function chosen from the urethane, urea, amide, hydrazide or oxamide functions.
- Rc represents a saturated, linear, aliphatic, hydrocarbon chain.
- Rc represents a hydrocarbon chain comprising from 4 to 18 carbon atoms, preferably from 4 to 14 carbon atoms, preferably from 4 to 12 carbon atoms, preferably from 4 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, preferably 6 to 8 carbon atoms.
- Rc is independently chosen from the groups -C 4 H 8- , -C 5 H l0- , -C 6 H 12- , -C 7 H 14- , -C 8 H 16- , -C 9 H 18- , -C 10 H 20- , -CnH 22- , C12H24, C13H26, C14H28, C15H30, - C I6 H3 2— , -C17H34-, -C 18 H 36 .
- Rc is independently chosen from the groups - C 4 H8 - , - C 6 Hi2 - , - C S H I ⁇ -, - C IO H 20 - , - Ci2H2 4 - , - C I4 H 2 8 - , - Ci ô ffe-,
- Rc is independently chosen from the groups -C 6 H I2- , -C 3 ⁇ 4 H
- R A and R B represent a hydrocarbon chain comprising from 4 to 150 carbon atoms or an oligomer chosen from polyolefins, polyetheroxides, polyacrylates, polymethacrylates, polysulfids, polystyrenics, polybutadienes, polyisobutenes, polyisoprenes, polyesters, polyamides, polysiloxanes, polyvinyl chlorides (PVC), polytetrafluoroethylenes (PTFE).
- PVC polyvinyl chlorides
- PTFE polytetrafluoroethylenes
- R A and R B which are identical or different, represent a hydrocarbon chain chosen from octadecyl, oleyl, hexadecyl, tetradecyl, pentadecyl, heptadecyl, cicosylc, dodecyl, tridecyl, undecyl.
- X and X ’ identical or different, represent a urethane or urea function.
- X and X ’ are identical and represent a urea function.
- the bituminous composition according to the invention advantageously comprises from 0.1 to 30% by mass of one or more molecules of general formula (I), preferably from 0.5 to 20%, preferably from 1 to 10%, more preferably from 2 to 10%, even more preferably from 2 to 5%, by mass relative to the total mass of the bituminous composition.
- the invention also relates to the use of at least one molecule according to the invention corresponding to the general formula (I) for preparing bituminous compositions, advantageously bituminous compositions in solid form at room temperature and in divided form.
- the invention relates in particular to a process for preparing a bituminous composition which comprises the following stages:
- bituminous binder comprising at least one bitumen
- bituminous composition in divided form, and in particular in the form of breads or granules.
- bitumen is chosen from bitumens of natural origin, from bitumens obtained from the refining of crude oil such as atmospheric distillation residues, vacuum distillation residues, visbreaked residues, blown residues, their mixtures and their combinations or among synthetic bitumens.
- the invention also relates to a solid bituminous composition at room temperature and in divided form.
- said bituminous composition is in the form of granules or breads.
- Another aspect of the invention relates to a method of transport and / or storage and / or handling of the bituminous composition, said bituminous composition being transported and / or stored and / or handled at room temperature in divided and solid form, in particular in the form of breads or solid granules.
- the invention also relates to the use of the solid bituminous composition at ambient temperature and preferably in divided form in the fields of road applications, in particular in the manufacture of road binders, mixes and roadways in general, and in the fields of industrial applications.
- the invention finally relates to a molecule corresponding to the general formula (I) as defined above and in detail below, and its use for preparing a bituminous composition, in particular for preparing a solid bituminous composition at room temperature and under divided form.
- the invention relates in particular to a molecule chosen from those corresponding to the following formulas:
- n 15 to 30.
- the invention also relates to the use of bituminous compositions as defined above and in detail below, in the fields of road applications, optionally in admixture with aggregates or aggregates of recycled bituminous mixes, in particular for manufacturing a surface coating, a hot mix, a cold mix, a cold mix, a severe emulsion, a base layer, a bonding layer, a bonding layer, a wearing course, an anti-omiant layer , a draining mix, or an asphalt, and in the fields of industrial applications, in particular for preparing a waterproofing coating, a membrane or an impregnation layer.
- the expression "between X and Y" includes the limits, unless explicitly stated otherwise. This expression therefore means that the target interval includes the values X, Y and all the values going from X to Y.
- oligomer is meant a macromolecule made up of a limited number of repeating units. These repeat units can all be the same or an oligomer can comprise different repeat units. Generally an oligomer comprises from 2 to 100 repeat units and an average molar mass greater than or equal to 200 g / mol and less than or equal to 20,000 g / mol, preferably less than or equal to 10,000 g / mol.
- bituminous composition according to the invention and its preparation process
- bituminous compositions according to the invention comprise at least one bitumen and at least one molecule of general formula (I):
- Rc represents a hydrocarbon chain comprising from 4 to 26 carbon atoms and optionally comprising one or more heteroatoms
- R A and R b identical or different, represent a hydrocarbon group comprising from 4 to 200 carbon atoms, and optionally comprising one or more heteroatoms,
- - X and X ' identical or different, represent a chemical function chosen from the urethane functions -0- (CO) -NH-, urea -HN- (CO) -NH-, amide - (CO) -NH-, hydrazide - (CO) - NH-NH- or oxamide -HN- (CO) - (CO) -NH-.
- Rc comprises one or more heteroatoms, advantageously these are chosen from O, N and S.
- Rc represents a hydrocarbon chain, aliphatic, linear, saturated.
- Rc represents a hydrocarbon chain comprising from 4 to 18 carbon atoms, preferably from 4 to 14 carbon atoms, preferably from 4 to 12 carbon atoms. carbon, preferably from 4 to 10 carbon atoms, preferably from 4 to 8 carbon atoms, preferably from 6 to 8 aromas.
- Rc represents a hydrocarbon chain comprising 4, 5, 6, 7 or 8 carbon atoms.
- Rc is chosen from the groups— C 4 l3 ⁇ 4 - , - CsHio-, - C 6 Hi 2 - , - C 7 H I4— , - C S H I ⁇ -, - CgHis -, - CioFLo-, - CnH 22 - , C 12 H 24 , C 13 H 26 , C 14 H 28 , -C 15 H 30- , C l6 H 32 , - C 17 H 34— , C I8 FI 36 .
- R c is chosen from the groups -C 4 H 8- , -C 6 H I2 -, -C 8 H I6 -, -C 10 H 20 -, -C 12 H 24 -, -C 14 H 28 - , -C I6 H 32 -, -C I8 H 36-; preferably from the groups -C 6 H I2 -, -C 8 H I6 -, -C IO H 2O _ , -Ci 2 H 24 _ , -C
- hydrocarbon chains aliphatic or aromatic, linear or branched, saturated or unsaturated, acyclic or cyclic, comprising from 4 to 200 carbon atoms and optionally comprising one or more heteroatoms,
- - oligomers soluble in bitumen comprising from 4 to 200 carbon atoms and optionally comprising one or more heteroatoms.
- R A and R B comprise one or more heteroatoms, advantageously these are chosen from O, N, S, Si, and the halogens, in particular F and Cl.
- R A and R B identical or different, represent a hydrocarbon chain, aliphatic or aromatic, linear or branched, saturated or unsaturated, acyclic or cyclic, comprising from 4 to 150 carbon atoms, preferably from 4 to 100 carbon atoms, preferably from 4 to 68 carbon atoms, preferably from 10 to 54 carbon atoms, preferably from 10 to 36 carbon atoms.
- R A and R B identical or different, represent a hydrocarbon chain comprising from 10 to 36 carbon atoms, more preferably from 16 to 20 carbon atoms.
- R A and R B represent a hydrocarbon chain chosen from octadecyl, oleyl, hexadecyl, tetradecyl, pentadecyl, heptadecyl, eicosyl, dodecyl, tridecyl, l 'undecyl.
- R A and R B which are identical or different, represent an oligomer soluble in bitumen.
- R A and R b which may be identical or different, are chosen from polyolefins such as polyethylene (PE), polypropylene (PP), polyethylene butylene (PEB), polyisobutene; polyetheroxides such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethyloxide (PTMO); polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutylacrylate (PABu); polysulfids; polystyrenics such as polystyrene (PS); polybutadienes and polyisoprenes; polyesters such as poly-e-caprolactone (PCL), polylactic acid (PL A); polyamides; polysiloxanes; halogenated polymers such as polyvinyl chloride (PVC), polytetra
- X and X ’ represent a urethane or urea function.
- X can represent a urea function and X ’a urethane function or vice versa.
- the two functions X and X ’ can be identical and represent a urea function.
- the two functions X and X ’ can be identical and represent a urethane function.
- X and X ’ are identical and represent a urea function.
- the molecule of formula (I) according to the invention can be described as comprising a central segment functionalized by two functions X and X 'chosen from the urea and / or urethane and / or amide and / or hydrazide and / or oxamide functions and two external segments (RA, RB) connected to the central segment by the functions X and X '.
- the molecule of formula (I) has a molar mass less than or equal to 20,000 g.mof 1 , preferably between 100 and 10,000 g.mol 1 .
- the molecule of formula (I) according to the invention has a molar mass of between 100 and 2000 g.mol 1 , preferably between 100 and 1000 g.mol 1 , more preferably between 100 and 500 g .mol 1 .
- organogelator or “organogelator molecule”, within the meaning of the invention, is meant a compound capable of establishing an association between several molecules of identical or different chemical structures to form a supramolecular network.
- organogelling molecules are capable of establishing physical interactions between them leading to self-aggregation with the formation of a 3D supramolecular network which is responsible for the gelling of bitumen.
- the stack of organogelling molecules allows the formation of a network of fibrils, immobilizing the molecules of the bitumen. The formation of fibrils can be observed for example by polarized optical microscopy, by scanning electron microscopy (SEM) ...
- the molecules of formula (I) according to the invention comprise a central segment comprising functions capable of creating hydrogen bonds. Said central segment is linked to external segments (R A , R B ) making it possible to promote the solubility of the molecule (I) in the bitumen.
- R A , R B external segments
- the molecules of formula (I) bind to each other non-covalently, in particular by hydrogen bonds. These hydrogen bonds disappear when the bitumen is heated to a high temperature.
- the assembly consisting of a large number of molecules of formula (I) can be assimilated to a “supramolecular” polymer and gives the bitumen thus modified improved properties.
- the gelation due to the aggregation of the molecules of formula (I), causes a thickening of the bituminous medium, leading to an increase in hardness, which allows the bituminous compositions according to the invention to be solid at ambient temperature.
- the hardness of these additive bituminous compositions, at use temperatures, is increased compared to the non-additive starting bitumen.
- the bituminous composition is heated, the interactions between the molecules (I) are weakened, and the bitumen regains the properties of a non-additive bitumen, the viscosity of the hot bituminous composition becomes again that of the starting bitumen. This phenomenon is also described in the present invention by the terminology "thermoreversible network”.
- bitumen compositions according to the invention essentially consist of:
- the granules according to the invention preferably comprise essentially:
- bitumen a) 70% to 99.9% of bitumen
- the granules according to the invention preferably comprise essentially:
- bituminous compositions according to the invention comprise at least one bitumen and at least one molecule of general formula (I).
- bituminous compositions according to the invention advantageously comprise from 0.1 to 30% by mass of one or more molecules of general formula (I), preferably from 0.5 to 20%, preferably from 1 to 10%, more preferably from 2 to 10%, even more preferably from 2 to 5% by mass relative to the total mass of the bituminous composition.
- the process for preparing the bituminous composition according to the invention advantageously comprises the following steps:
- bituminous binder comprising at least one bitumen
- bituminous composition in divided form, and in particular in the form of breads or granules.
- bituminous binder means a bitumen alone, and optionally comprising additives such as a polymer and / or a fluxing agent.
- the bituminous binder can be in anhydrous form or in the form of an emulsion.
- the process for preparing the bituminous compositions according to the invention comprises the following steps:
- bitumen is introduced into a container fitted with mixing means, and the bitumen is brought to a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C, preferably between 110 and 180 ° C,
- bituminous composition obtained from step b) is heated to a temperature between 70 and 220 ° C, preferably between 90 and 180 ° C , preferably between 110 and 180 ° C., with stirring, until a bituminous composition, advantageously homogeneous, is obtained, d) optionally the bituminous composition resulting from step c) is shaped in divided form, and especially in the form of breads or granules.
- bituminous compositions according to the invention can contain bitumens originating from different origins.
- bitumens which can be used according to the invention, mention may be made first of all of the bitumens of natural origin, those contained in deposits of natural bitumen, of natural asphalt or the oil sands and the bitumens originating from the refining of crude oil.
- the bitumens according to the invention are advantageously chosen from the bitumens originating from the refining of crude oil.
- the bitumens can be chosen from the bitumens or mixtures of bitumens originating from the refining of crude oil, in particular bitumens containing asphaltenes or pitches.
- Bitumens can be obtained by conventional methods of manufacturing bitumens in refineries, in particular by direct distillation and / or distillation under oil vacuum. These bitumens may be optionally visbreaked and / or deasphalted and / or air-rectified. It is common to carry out vacuum distillation of atmospheric residues from the atmospheric distillation of crude oil. This manufacturing process therefore corresponds to the succession of atmospheric distillation and vacuum distillation, the feedstock feeding the vacuum distillation corresponding to atmospheric residues. These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a charge usually composed of distillates and heavy products from vacuum distillation of atmospheric residues from petroleum distillation.
- bitumens or bitumen bases obtained by the refining processes can be combined together to obtain the best technical compromise.
- Bitumen can also be recycled bitumen.
- the bitumens can be hard grade or soft grade bitumens.
- bitumen is chosen from bitumens of natural origin, from bitumens resulting from the refining of crude oil such as atmospheric distillation residues, vacuum distillation residues, visbreaked residues, blown residues, their mixtures and their combinations or among the synthetic bitumens otherwise known as clear binders.
- the bitumen may also comprise at least one polymer and / or a fluxing agent.
- polymers for bitumen mention may be made of elastomers such as copolymers SB, SBS, SIS, SBS *, SBR, EPDM, polychloroprene, polynorbomene and optionally polyolefins such as polyethylenes PE, HDPE, polypropylene PP , plastomers such as EVA, EMA, copolymers of olefins and unsaturated carboxylic esters EBA, elastomeric polyolefin copolymers, polybutene of the polybutene type, copolymers of ethylene and of acrylic acid esters, methacrylic or maleic anhydride, copolymers and terpolymers of ethylene and glycidyl methacrylate, ethylene-propylene copolymers, rubbers, polyisobutylenes, SEBS, ABS.
- elastomers such as copolymers SB, SBS, SIS, SBS *, SBR, EPDM, polych
- additives can also be added to the bitumen according to the invention. They are, for example, vulcanizing agents and / or crosslinking agents capable of reacting with a polymer, when it is an elastomer and / or a plastomer, which can be functionalized and / or which may include reactive sites.
- vulcanizing agents mention may be made of those based on sulfur and its derivatives, used to crosslink an elastomer at contents of 0.01% to 30% by mass relative to the mass of elastomer.
- crosslinking agents such as mono or polyacids, or carboxylic anhydrides, esters of carboxylic acids, sulfonic, sulfuric, phosphoric acids, even acid chlorides, phenols , at contents of 0.01% to 30% mass relative to the mass of polymer. These agents are capable of reacting with the elastomer and / or the functionalized plastomer. They can be used in addition to or as a replacement for vulcanizing agents.
- bituminous composition according to the invention can also comprise as additive an olefinic polymeric adjuvant.
- the olefin polymer adjuvant is preferably chosen from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers and (b) ethylene / monomer A / monomer B terpolymers:
- the ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from random or block, preferably statistical, copolymers of ethylene and of a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by mass, preferably from 60% to 95% by mass, more preferably 60% to 90% by mass of ethylene,
- the terpolymers are advantageously chosen from random or block, preferably random, terpolymers of ethylene, of a monomer A and of a monomer B.
- the monomer A is chosen from vinyl acetate and C1 to C6 alkyl acrylates or methacrylates.
- the monomer B is chosen from glycidyl acrylate and glycidyl methacrylate.
- the ethylene / monomer A / monomer B terpolymers advantageously comprise from 0.5% to 40% by mass, preferably from 5% to 35% by mass, more 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 originating from monomer B, the remainder being formed from units originating from ethylene.
- the olefinic polymer adjuvant is chosen from random terpolymers of ethylene (b), of a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and of a monomer B chosen from acrylate. of glycidyl and glycidyl methacrylate, comprising from 0.5% to 40% by mass, preferably from 5% to 35% by mass, more preferably from 10% to 30% by mass of units originating from monomer A and, from 0.5% to 15% by mass, preferably from 2.5% to 15% by mass of units originating from monomer B, the remainder being formed of units from ethylene.
- the bituminous composition solid at room temperature and preferably in divided form of the invention may comprise from 0.05% to 15% by mass, preferably from 0.1% to 10% by mass, more preferably from 0.5% to 6% by mass of the olefinic polymeric adjuvant relative to the total mass of the bituminous composition according to the invention.
- the bituminous composition which is solid at room temperature and preferably in divided form can also comprise between 0.5% and 20% by mass, preferably between 2% and 20% by mass, more preferably between 4 % and 15% of one or more anti-caking compounds by mass relative to the total mass of the bituminous composition according to the invention.
- anti-caking agent or “anti-caking compound” means any compound which limits, reduces, inhibits, delays, the agglomeration and / or the adhesion of the granules to one another during their transport and / or their storage at ambient temperature and which ensures their fluidity during their handling.
- the anti-caking compound is chosen from: talc; fines generally less than 125 ⁇ m in diameter, such as siliceous fines, with the exception of limestone fines; sand such as Fontainebleau sand; cement ; carbon; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular pine; rice husk ash; glass powder; clays such as kaolin, bentonite, vermiculite; alumina such as alumina hydrates; silica; silica derivatives such as silica fumes, functionalized silica fumes, in particular hydrophobic or hydrophilic silica fumes, fumed silicas, in particular hydrophobic or hydrophilic fumed silicas, silicates, silicon hydroxides and silicon oxides ; plastic powder; lime; hydrated lime; the plaster ; rubber crumb; polymer powder, such as styrene
- G anti-caking agent is chosen from talc; fines generally of diameter less than 125 ⁇ m with the exception of limestone fines, such as siliceous fines; wood residues such as lignin, lignosulfonate, powders of coniferous needles, powders of coniferous cones, in particular pine; glass powder; sand like sand from fontainebleau; silica fumes, in particular hydrophobic or hydrophilic silica fumes; fumed silicas, in particular hydrophobic or hydrophilic fumed silicas; and their mixtures.
- bituminous composition according to the invention is solid at room temperature and in divided form. According to a preferred embodiment, the bituminous composition according to the invention is in the form of granules or breads.
- the granules according to the invention are obtained by shaping the bituminous composition according to the invention as described above according to any known method, for example according to the manufacturing method described in document US 3,026,568, document WO 2009/153324 or WO 2012/168380.
- the methods described in application WO2018 / 104660 can be used.
- the shaping of the granules can be carried out by draining, in particular using a drum.
- the bread according to the invention according to the invention can be produced according to any known process, for example according to the manufacturing process described in document US2011 / 0290695.
- bituminous composition according to the invention is in the form of granules.
- the granules according to the invention may have, within the same population of granules, one or more shapes chosen from a cylindrical, spherical or ovoid shape.
- the granules according to the invention preferably have a cylindrical or spherical shape.
- the size of the granules according to the invention is such that the longest average dimension is preferably less than or equal to 50 mm, more preferably from 3 to 30 mm, even more preferably from 5 at 20 mm.
- the use of a die makes it possible to control the manufacture of granules of a chosen size.
- a sieving makes it possible to select granules according to their size.
- the granules according to the invention have a weight of between 0.1 g and 50 g, preferably between 0.2 g and 10 g, more preferably between 0.2 g and 5 g.
- the size of the granules according to the invention is such that the longest average dimension is preferably less than or equal to 20 mm, more preferably less than or equal to 10 mm, even more preferably less than or equal to 5 mm.
- bituminous composition solid at room temperature and in divided form according to the invention preferably in the form of granules, is covered on at least part of its surface, or even the whole of its surface with a anti-caking agent, preferably of mineral or organic origin, more preferably of mineral origin.
- the mass of anti-caking agent G covering at least part of the surface of the granules is advantageously between 0.2% and 10% by mass, preferably between 0.5% and 8% by mass, more preferably between 0.5% and 5% relative to the total mass of said granules according to the invention.
- the anti-caking compound covers at least 50% of the surface of the granules, preferably at least 60%, preferably at least 70%, more preferably at least 80% and even more preferably at least 90% .
- the anti-caking agent is as defined above in the description.
- the anti-caking compound used to cover at least part of the surface of the granules is chosen from the molecules of formulas (I), advantageously in the form of powder.
- the average thickness of the anti-caking layer is greater than or equal to 20 mhi, more preferably between 20 and 100 mhi.
- G anti-caking agent included in the granules can be identical or different from G anti-caking agent covering at least part of the surface of said granules.
- the bituminous composition according to the invention is in the form of bread.
- Bread is understood to mean a block of the bituminous composition having a mass of between 0.1 kg and 1000 kg, preferably between 1 kg and 200 kg, more preferably between 1 kg and 50 kg, even more preferably between 5 kg and 35 kg, even more preferably between 10 kg and 30 kg, said block being advantageously parallelepipedic, preferably being a block.
- the bread according to the invention preferably has a volume of between 100 cm 3 and 50,000 cm 3 , preferably between 5,000 cm 3 and 25,000 cm 3 , more preferably between 10,000 cm 3 and 30,000 cm 3 , even more preferably between 14,000 cm 3 and 25,000 cm 3 .
- the mass of said bread can vary from 1 to 20 kg, and from 20 to 50 kg in the case of handling by two people.
- the mass of the bread can vary from 50 to 1000 kg.
- the bread according to the invention can be manufactured according to any known process, for example according to the manufacturing process described in document US2011 / 0290695.
- the bread according to the invention is advantageously packaged with a hot-melt film put in place according to any known process, preferably by a film of polypropylene, of polyethylene or a mixture of polyethylene and polypropylene.
- the bituminous composition packaged in bitumen bread wrapped in a hot-melt film has the advantage of being ready for use, that is to say that the bitumen bread can be directly heated in the melter or optionally introduced directly in the asphalt mixing unit for the manufacture of asphalt, without unpacking beforehand.
- the hot-melt film which melts with the bituminous composition according to the invention does not affect its properties.
- the bread according to the invention can also be packaged in a carton according to any known process.
- the bread according to the invention is packaged in a carton by hot pouring the bituminous composition according to the invention into a carton whose wall of the internal face is silicone-coated and then cooled, the dimensions of the carton being adapted to the weight and / or the volume of the bread according to the invention desired.
- the Applicant has demonstrated that the deterioration of said hot-melt film or of said carton during transport and / or storage at room temperature and even at room temperature high of said bread did not cause the creep of the bread according to the invention. Consequently, the breads according to the invention retain their initial shape and do not stick together during their transport and / or storage at high ambient temperature despite the fact that the hot-melt film or the cardboard is damaged.
- the Applicant considers that the absence of creep of the solid bituminous composition at room temperature and in the form of granules or bread during its transport and / or storage at room temperature, in particular high is due to the formulation of the bituminous composition according to the invention and in particular to the presence of at least one molecule of general formula (I) according to the invention within the bituminous composition.
- the invention also relates to a method of transport and / or storage and / or handling of the bituminous composition, said bituminous composition being transported and / or stored and / or handled at room temperature in divided and solid form, in particular in the form of breads or solid granules.
- said solid bituminous composition at ambient temperature and in divided form according to the invention is transported and / or stored and / or handled at ambient temperature, in particular at elevated ambient temperature, for a period greater than or equal to 2 months, preferably at 3 months.
- ambient temperature is meant the temperature at which bitumen is used, it being understood that ambient temperature implies that no heat is supplied other than that resulting from climatic conditions.
- the ambient temperature can reach high values, below 100 ° C during the summer periods, in particular in the geographical regions with hot climate.
- the ambient temperature is less than 100 ° C.
- the ambient temperature is from 20 ° C to 50 ° C, preferably from 25 ° C to 50 ° C, preferably from 25 ° C to 40 ° C.
- the high ambient temperature is from 40 ° C to 90 ° C, preferably from 50 ° C to 85 ° C even more preferably from 50 ° C to 75 ° C, even more preferably from 50 ° C to 60 ° C.
- bituminous compositions which are solid at room temperature and in divided form according to the present invention are remarkable in that they are solid at room temperature and therefore easy to handle, even at high ambient temperatures.
- the bituminous compositions solid at room temperature and in divided form according to the present invention also allow the transport and / or storage and / or handling of said granules or breads at room temperature under optimal conditions, in particular without creep said granules or breads during their transport and / or their storage and / or their handling, even when the ambient temperature is high and without degrading the properties of said bituminous composition, or even by improving them.
- bituminous compositions according to the invention are envisaged in the fields of road applications, in particular in the manufacture of road binders, mixes and pavements in general, and in the fields of industrial applications.
- the solid bituminous composition at room temperature, in particular in divided form, according to the invention in various road applications, optionally in admixture with aggregates to produce a surface coating, a hot mix, a cold mix. , a cold-cast mix, a severe emulsion, a base coat, a bonding layer, a bonding layer or a wearing course.
- These applications are aimed in particular at bituminous mixes as materials for the construction and maintenance of pavement bodies and their coating, as well as for the performance of all road works. Mention may be made of other associations of the bituminous composition and of the aggregate having particular properties, such as anti-omiant layers, draining mixes, or asphalts (mixture between a bituminous binder and aggregates of the sand type).
- bitumen granules according to the invention are particularly suitable for the manufacture of waterproofing membranes, anti-noise membranes, insulation membranes, surface coatings, carpet tiles or even impregnation layers.
- the invention also relates to a process for the manufacture of coated materials comprising at least the bituminous composition which is solid at room temperature, in particular in the divided form according to the invention and aggregates or aggregates of recycled bituminous coated materials, this method comprising at least the steps from:
- the process for the manufacture of mixtures according to the invention advantageously does not require a step of heating the bituminous composition according to the invention before mixing with the recycled mixtures of aggregates or the aggregates because in contact with the mixture of hot aggregates or on contact with the hot aggregate mixture, the bituminous composition according to the invention solid at ambient temperature melts.
- the subject of the invention also relates to the molecule of formula (I):
- bituminous composition The preferential choices for the bituminous composition are the same for the molecule of formula (I).
- the molecules of general formula (I) can be synthesized by any method known to those skilled in the art.
- a diisocyanate and a precursor of the external chains can be brought into contact under conditions allowing an addition or polyaddition reaction between the reagents to form the molecule of formula (I ).
- Said external chain precursor can be functionalized by a function chosen from alcohol, thiol or amine functions, preferably alcohol or amine.
- external chain precursor can be a compound of formula R A -OH, R A -NH 2 , R B -OH, R B -NH 2 , OR a mixture of these compounds.
- the synthesis is carried out in the presence of a solvent.
- the solvent can be chosen from organic solvents. Aprotic organic solvents are preferred. Mention may be made of tetrahydrofuran (THF), dimethylformamide (DMF), dichloromethane, chloroform, etc.
- the synthesis can be carried out at a temperature between 20 and 200 ° C, more preferably between 20 and 100 ° C, more preferably between 20 and 60 ° C for a time ranging from 5 minutes to 24 hours, preferably 2 hours at 8 o'clock.
- the molar ratios between the reagents and the order of addition of said reagents are controlled to obtain the desired molecule of formula (I).
- the nature of the precursor of the external chain (R A , R b ) can also be controlled, as well as its functionalization to obtain the desired functions X and X '.
- FTIR Fourier transform infrared spectrometry
- NMR Nuclear Magnetic Resonance
- DSC Differential scanning calorimetry
- bitumens or bituminous compositions comprising the molecules of formula (I) to which reference is made in these examples are measured according to the methods indicated in Table 1.
- bitumen base of grade 70/100 denoted B 0 , having a penetration P 25 of 82 1/10 mm and a TBA of 46 ° C and commercially available from Total Marketing Services.
- FTIR - ATR (cm 1 ): 3328, 2925, 2851, 1611, 1579.
- bituminous additive compositions are prepared by introducing the bitumen base B 0 and the molecule in the proportions reported in Table 2 below into a reactor with stirring and at 170 ° C. The mixtures are stirred and heated at 170 ° C for about 30 minutes. Table 2
- Table 3 below presents the physical characteristics of the bituminous compositions according to the invention Ci and C 2 and controls To and Ti.
- compositions according to the invention Ci and C 2 have properties superior to the bitumen alone To , but also superior to the composition Ti added with sebacic acid at 5% by mass relative to the total mass of the bituminous composition.
- An increase in TB A is noted for the compositions according to the invention to a value going beyond 150 ° C.
- This TBA value is much higher than the TBA value of the comparative composition Ti which is 102 ° C. This reflects a higher consistency of the compositions Ci and C 2 according to the invention.
- composition according to the invention Ci has a viscosity at 180 ° C equivalent to that of the pure bitumen T 0 , and that of the composition Ti.
- compositions according to the invention therefore have a good consistency at the temperatures of use and are moreover sufficiently fluid at the temperatures of application, thus allowing a good coating of the aggregates and a placement of the mixes on the road easier with the means. current techniques of the road profession.
- Example 2 Preparation of bitumen breads
- Bitumen breads Po, PTI, PCI and P C2 are prepared according to the following method, respectively from the bitumen alone B 0 , and from the control compositions Ti and the compositions according to the invention Ci and C 2 .
- a mass of about 0.5 kg of bitumen is poured at 160 ° C into a rectangular steel mold covered with a hot melt polyethylene film. The mold is then cooled to room temperature and then removed from the mold.
- the test is carried out at a temperature of 70 ° C. and with a shear stress of 100 Pa with a shear rheometer of the MCR301® type from the Anton Paar brand.
- a 25 mm diameter plane-plane geometry module is used.
- the analysis is carried out as follows: the sample is crushed at 70 ° C between the two plates to a gap of 1.025 mm, the excess is leveled and the gap is adjusted to 1 mm (value used for analysis).
- a waiting time of 10 min allows the sample to be homogeneous in temperature and then the measurement begins.
- Figure 1 lists the results of the deformation as a function of time obtained for the different bitumen breads.
- the deformation (without unit) is reported on the Y axis and the time in seconds is reported on the X axis.
- the curve in solid line represents that of the bread P 0 ;
- the curve in dotted lines (-) represents that of bread P Ti ;
- the curve with the circles (-O-) represents that of bread P C2 ;
- the curve with the triangles (-D-) represents that of the bread
- This test is carried out in order to assess the compressive strength of each P o , PTI, PCI bread when it is subjected to a load and at a temperature of 50 ° C.
- the compression resistance test proper is carried out using a texture analyzer marketed under the name LF Plus by the company LLOYD Instruments and equipped with a thermal enclosure. To do this, a metal and cylindrical box containing a mass of 60 g of bitumen bread is placed inside the thermal enclosure set to a temperature of 50 ° C.
- the texture analyzer piston is a cylinder with a diameter of 20 mm and a height of 60 mm. The cylindrical piston is initially placed in contact with the upper surface of the bitumen bar. Then, it moves vertically downwards, at a constant speed of 1 mm / min, over a calibrated distance of 10 mm so as to exert a compressive force on the upper surface of the bitumen bread.
- the texture analyzer measures the maximum compression force applied by the piston to the bitumen bar at 50 ° C.
- the measurement of the maximum compression force makes it possible to evaluate the capacity of the bitumen roll to resist deformation.
- the greater this force the better the resistance to deformation of the bitumen bread.
- the Pci breads according to the invention are particularly resistant to compression compared to the control bitumen breads Po based on bitumen alone and Pu based on bitumen additivated with sebacic acid.
- the bread P Ci according to the invention is remarkable in that the maximum compression force is approximately 37 times greater than that applied to the control bitumen breads Po and approximately 1.6 times greater than that applied to the bitumen breads Rci based on bitumen additive to sebacic acid.
- bitumen breads according to the invention do not stick together and keep their shape and consistency even at high ambient temperature. Transport and / or storage are therefore optimized for the bitumen rolls according to the invention, with easier, safer handling and minimized bitumen losses.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1857590A FR3085170B1 (fr) | 2018-08-22 | 2018-08-22 | Composition bitumineuse thermoreversible |
PCT/FR2019/051930 WO2020039138A1 (fr) | 2018-08-22 | 2019-08-19 | Composition bitumineuse thermoreversible |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3841164A1 true EP3841164A1 (fr) | 2021-06-30 |
Family
ID=63896405
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19782650.6A Pending EP3841164A1 (fr) | 2018-08-22 | 2019-08-19 | Composition bitumineuse thermoreversible |
Country Status (5)
Country | Link |
---|---|
US (1) | US20210171453A1 (fr) |
EP (1) | EP3841164A1 (fr) |
CA (1) | CA3109547A1 (fr) |
FR (1) | FR3085170B1 (fr) |
WO (1) | WO2020039138A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112280473A (zh) * | 2020-10-14 | 2021-01-29 | 上海东方雨虹防水技术有限责任公司 | 一种改性沥青涂盖料和改性沥青防水卷材 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3026568A (en) | 1958-11-14 | 1962-03-27 | Schuller Services Ltd | Method for producing coated bitumen pellets |
CA1260653A (fr) * | 1985-04-11 | 1989-09-26 | Richard T. Janicki | Asphalte modifie |
FR2911611B1 (fr) | 2007-01-23 | 2011-01-07 | Total France | Composition bitumineuse aux proprietes thermoreversibles. |
CN102066068B (zh) | 2008-06-20 | 2017-06-20 | 国际壳牌研究有限公司 | 涂覆粘合剂单元的制备方法 |
SG163463A1 (en) | 2009-02-03 | 2010-08-30 | Eps Offshore Oil Trading Plc | Consumable bitumen film for packaging bitumen |
SG195267A1 (en) | 2011-06-07 | 2013-12-30 | Shell Int Research | Method for preparing coated binder units |
FR3024456B1 (fr) | 2014-08-01 | 2016-08-19 | Total Marketing Services | Granules de bitume routier |
FR3059674B1 (fr) | 2016-12-07 | 2018-11-23 | Total Marketing Services | Bitume solide a temperature ambiante |
-
2018
- 2018-08-22 FR FR1857590A patent/FR3085170B1/fr active Active
-
2019
- 2019-08-19 EP EP19782650.6A patent/EP3841164A1/fr active Pending
- 2019-08-19 CA CA3109547A patent/CA3109547A1/fr active Pending
- 2019-08-19 WO PCT/FR2019/051930 patent/WO2020039138A1/fr active Application Filing
- 2019-08-19 US US17/270,111 patent/US20210171453A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CA3109547A1 (fr) | 2020-02-27 |
FR3085170B1 (fr) | 2021-06-04 |
US20210171453A1 (en) | 2021-06-10 |
FR3085170A1 (fr) | 2020-02-28 |
WO2020039138A1 (fr) | 2020-02-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3174925B1 (fr) | Granules de bitume routier | |
EP3559136B1 (fr) | Composition d'asphalte coulé pour la réalisation de revêtements | |
WO2018104660A1 (fr) | Bitume solide a temperature ambiante | |
EP3510105B1 (fr) | Composition bitumineuse pour enrobes a module eleve | |
EP3307830A1 (fr) | Bitume solide a temperature ambiante | |
WO2018046838A1 (fr) | Liant clair solide a froid | |
WO2019211560A1 (fr) | Composition bitume/polymere presentant des proprietes mecaniques ameliorees | |
FR3065465B1 (fr) | Bitume solide a temperature ambiante | |
EP3841164A1 (fr) | Composition bitumineuse thermoreversible | |
WO2018046839A1 (fr) | Bitume solide a temperature ambiante | |
EP3841163A1 (fr) | Composition bitumineuse thermoreversible | |
EP3841165A1 (fr) | Composition bitumineuse thermoreversible | |
EP3894469B1 (fr) | Granules de bitume solides a temperature ambiante | |
WO2017203154A1 (fr) | Bitume solide a temperature ambiante | |
EP3894468B1 (fr) | Bitume solide a temperature ambiante | |
RU2799545C2 (ru) | Термообратимая битумная композиция | |
OA19430A (fr) | Bitume solide à température ambiante. | |
OA19552A (en) | Bituminous composition for high modulus Mixes. | |
OA19100A (fr) | Bitume solide à température ambiante. | |
OA19429A (fr) | Procédé de préparation de bitume solide à température ambiante en lit d'air fluidisé. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210223 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: SORBONNE UNIVERSITE Owner name: TOTALENERGIES ONETECH |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20230821 |