EP3440130A1 - Procede de preparation d'une composition bitume / polymere presentant des proprietes ameliorees - Google Patents
Procede de preparation d'une composition bitume / polymere presentant des proprietes amelioreesInfo
- Publication number
- EP3440130A1 EP3440130A1 EP17721775.9A EP17721775A EP3440130A1 EP 3440130 A1 EP3440130 A1 EP 3440130A1 EP 17721775 A EP17721775 A EP 17721775A EP 3440130 A1 EP3440130 A1 EP 3440130A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bitumen
- weight
- elastomer
- sbs
- ductility
- 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.)
- Withdrawn
Links
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- 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
- C08L2555/50—Inorganic non-macromolecular ingredients
- C08L2555/54—Sulfur or carbon black
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- 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 field of bitumens. More specifically, it relates to a process for preparing sulfur-crosslinked bitumen / polymer compositions for preparing compositions having improved oxidation resistance and ductility properties at the same time.
- the invention also relates to the use of bitumen / polymer compositions obtained by this method in the fields of road applications such as hot mixes; warm mixes; cold mixes, for example cold mixes or severe emulsions; or surface coatings, for example emulsions or fluxed bitumens; and in the fields of industrial applications, for example in the manufacture of interior and exterior coatings.
- bituminous compositions having improved properties and their method of preparation have been widely described in the literature.
- the random or block copolymers of styrene and of a conjugated diene and, in particular, styrene and butadiene or styrene and isoprene are known to be particularly effective because they mix very easily in the bitumens and give them excellent mechanical properties and in particular very good elastic properties.
- bitumen / polymer compositions are used for the preparation of binders for various surface coatings and, in particular, as road surface coatings, provided that these compositions have in combination a number of mechanical properties. Optimized mechanical characteristics such as elastic properties are particularly crucial for applications in road surfaces.
- bitumen composition It is also important to ensure the preservation of the properties of the bitumen composition, that it has a high resistance to oxidation. In some countries, particularly in Cuba, it is also essential to be able to produce bitumen compositions which have satisfactory ductility properties.
- target specification is:
- a ductility at 25 ° C. according to the ASTM D-113 standard greater than or equal to 80 cm, preferably greater than or equal to 100 cm, and
- thermoreiculated bitumen / polymer compositions comprising a block copolymer based on styrene and butadiene.
- sulfur crosslinking is preferable to heat-crosslinking to obtain good storage stability.
- the sulfur crosslinking of the bitumen / polymer compositions usually entails a greater rigidity than thermo-crosslinking. It is therefore more difficult to achieve satisfactory mechanical performance with sulfur crosslinking.
- the bitumen bases with high ductility have the disadvantage of having low mechanical properties, including low elastic recovery and low resistance to aging, which results in an increase in the TBA and significant reduction in penetrability. It was therefore desirable to incorporate elastomers which are known to improve mechanical properties and aging resistance.
- the invention relates to a method for preparing a bitumen / polymer composition.
- the invention relates to a process for producing a bitumen / polymer composition having a ductility at 25 ° C, according to ASTM D-113, greater than or equal to 80 cm and a ductility at 25 ° C, according to ASTM D -113, after aging RTFOT at 163 ° C. for 85 minutes, according to the ASTMD2872 standard, greater than or equal to 45 cm, this process comprising:
- elastomer 1 to 10% by weight of elastomer relative to the weight of the bitumen base, the elastomer being chosen from SBS elastomers and elastomer mixtures comprising at least 40% by weight of SBS,
- bitumen base is chosen from bases having ductility at 25 ° C, according to ASTM D-113, greater than or equal to 50 cm.
- the base is chosen from bitumen bases having a volatility after aging RTFOT greater than or equal to 0.20%> m / m, preferably greater than or equal to 0.30%> m / m.
- the elastomer is introduced in an amount ranging from 3 to 5% by weight relative to the weight of the bitumen base.
- the SBS copolymer is a Styrene-Butadiene-Styrene copolymer.
- the styrene content of the copolymer or copolymers is from 10% to approximately 40% by weight relative to the total weight of the copolymer or copolymer mixture.
- the weight average molecular weight of the SBS elastomer is between 10,000 and 600,000 daltons.
- the elastomer is chosen from SBS elastomers and elastomer mixtures comprising at least 50% by weight of SBS relative to the total mass of the mixture.
- the elastomer consists of SBS elastomers or SB and SBS elastomer mixtures.
- the elastomer is introduced in the form of granules.
- the sulfur-containing crosslinking agent comprises from 10 to 100% by weight of elemental sulfur and from 0 to 90% by weight of a sulfur-containing compound.
- the sulfur-containing crosslinking agent is introduced in the form of granules comprising a binder, in particular EVA.
- the bitumen / polymer composition has a ductility at 25 ° C., according to the ASTM D-113 standard, greater than or equal to 100 cm, and a ductility at 25 ° C., according to the ASTM D-113 standard. after aging RTFOT at 163 ° C for 85 minutes, according to ASTMD2872 standard, greater than or equal to 50 cm.
- the process comprises at least the steps of: i) heating the bitumen base to a temperature ranging from 100 ° C. to 250 ° C., ii) introducing into the reactor containing the bitumen base of: sulfur-crosslinkable elastomer, the sulfur-containing crosslinking agent and optionally an olefinic polymer adjuvant and additives,
- the invention also relates to a process for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold-cast mix, a serious emulsion, said binder being associated with aggregates and / or recycling costs, this process comprising at least the preparation of a bitumen / polymer composition according to the process defined above.
- the invention also relates to a process for preparing a sealing coating, a membrane or an impregnating layer, this process comprising at least the preparation of a bitumen / polymer composition according to the method defined above.
- bitumen / polymer composition and “bitumen / polymer binder” represent the same type of composition and are used interchangeably.
- the invention relates to bitumens. These can be formed by one or more bitumen bases.
- bitumen any bituminous compositions consisting of one or more bitumen bases and possibly comprising one or more chemical additives, said compositions being intended for a road application or an industrial application.
- bitumen bases that may be used according to the invention, mention may first be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. .
- the bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil.
- the bitumen bases may be chosen from bitumen bases or bitumen base mixtures derived from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches.
- the bitumen bases can be obtained by conventional processes for the manufacture of bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of the oil.
- bitumen bases may optionally be visbroken and / or deasphalted and / or rectified in air.
- Vacuum distillation of atmospheric residues from atmospheric distillation of crude oil is common. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a distillation under vacuum, the feed supplying the vacuum distillation corresponding to the 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 the vacuum distillation of atmospheric residues from the distillation of petroleum. This method provides a base blown, or semi-blown or oxidized or rectified in air or rectified partially in air.
- bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise.
- the bitumen base can also be a bitumen recycling base.
- the bitumen bases may be bitumen bases of hard grade or soft grade.
- production temperatures of between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C., are used, and stirring is carried out for a period of time. at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
- the term "manufacturing temperature” means the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by the standard NF EN 12594.
- the blown bitumens can be manufactured in a blowing unit, by passing a stream of air and / or oxygen through a starting bituminous base.
- This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
- the blowing is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long periods of time 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.
- Bitumen can also be a recycling bitumen.
- the bitumens may be hard grade or soft grade bitumens.
- the bitumens which can be used according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, of from 5 to 330 1/10 mm, preferably from 10 to 220 1/10 mm, more preferably from 10 to 120 1 / 10 mm.
- bitumens that can be used according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, of 50 to 70 1/10 mm.
- the so-called “needle penetration” measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C. (P25). This characteristic of penetrability is expressed in tenths of a millimeter (dmm or 1/10 mm).
- the needle penetration, measured at 25 ° C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, of a needle whose weight with its support is 100 g.
- the NF EN 1426 standard replaces the NF T 66-004 approved standard of December 1986 with effect from December 20, 1999 (decision of the Chief Executive Officer of AFNOR dated November 20, 1999).
- the invention applies more particularly to bitumen bases originating in South America, Central America, Mexico, the Caribbean and in particular Cuba. It also applies to bitumen bases with characteristics comparable to bitumen bases originating in South America, Central America, Mexico, the Caribbean and in particular Cuba.
- bitumen bases having ductility at 25 ° C according to ASTM D-113 greater than or equal to 80 cm, more particularly greater than or equal to 100 cm.
- these bitumen bases in general have mechanical properties, and aging resistance properties, insufficient.
- the RTFOT aging is carried out at 163 ° C. for 85 minutes according to the ASTMD2872 standard.
- the invention particularly relates to bases having a springback measured at 25 ° C according to EN13398 less than or equal to 20%. Indeed, these bases have insufficient elastic properties, which is reflected during their use in road applications including a low resistance to tearing, rutting and wear.
- the bases concerned are characterized by a volatility after RTFOT aging of greater than 0.20% m / m, which represents the maximum threshold according to European standards.
- the invention is particularly applicable to bitumen bases having an RTFOT volatility after aging greater than or equal to 0.20% w / w, preferably greater than or equal to 0.30% w / w.
- the elastomer :
- the elastomer is selected from sulfur crosslinkable block copolymers of the SBS type and mixtures of SBS block copolymers with other elastomers.
- the monovinylaromatic hydrocarbon groups designated S can be any monovinylaromatic hydrocarbon compound known for use in the preparation of block copolymers such as: styrene, ⁇ -methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4- dimethylstyrene, ralpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof.
- the preferred monovinyl aromatic hydrocarbon compound according to the present invention is styrene, which is used as a substantially pure monomer or as a major component in mixtures with minor proportions of another structurally related vinyl aromatic monomer, such as ⁇ -methylstyrene, p-methylstyrene, p-tert-butylstyrene 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, that is, in amounts of at most 10% by weight.
- the use of substantially pure styrene is particularly preferred in the present invention.
- the monovinyl aromatic hydrocarbon monomer content of the copolymer (s) (preferably the styrene content) is from about 10% to about 40% by weight based on the total weight of the copolymer or copolymer mixture.
- these elastomers and these elastomer mixtures are chosen in the form of granules which facilitates the handling of said elastomers or mixtures during the process for manufacturing a bitumen-polymer composition.
- the hydrocarbon groups B denote butadiene.
- 1,3-butadiene is polymerized via a 1,2-addition mechanism, the result is a pendant vinyl group relative to the polymer backbone.
- Polybutadiene is present in blocks or segments that contain different levels of vinyl.
- This vinyl content makes it possible to characterize the polymer.
- the vinyl content is greater than or equal to 5% by mass relative to the weight of B, preferably between 5 and 50% by mass relative to the weight of B.
- the weight average molecular weight of the SBS elastomer is advantageously between 10,000 and 600,000 daltons, preferably between 30,000 and 400,000 daltons, more preferably between 50,000 and 300,000 daltons.
- the molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to ASTM D5296-05.
- block copolymers used in the invention are well known to those skilled in the art and are commercially available, especially under the Kraton® and Sibur® brands.
- composition may comprise other elastomers than SBS terpolymers.
- composition according to the invention may contain other known bitumen elastomers such as copolymers SB (block copolymer of styrene and butadiene), SIS (styrene-isoprene-styrene), SBS * (styrene-block copolymer). star butadiene-styrene), SBR (styrene-b-butadiene rubber), EPDM (modified ethylene propylene diene), polychloroprene, polynorbomene, natural rubber, recycled rubber, polybutene, polyisobutylene, SEBS (styrene copolymer, ⁇ ethylene, butylene and styrene).
- copolymers SB block copolymer of styrene and butadiene
- SIS styrene-isoprene-styrene
- SBS * styrene-block copolymer
- the SBS block terpolymers represent at least 40% by weight of the total mass of the elastomers present in the composition, more preferably at least 50% by weight.
- the elastomer consists of one or more SBS block copolymers.
- the elastomer consists of one or more SBS block copolymers and one or more SB block copolymers.
- the SBS elastomer represents at least 40% by weight of the total mass of the elastomer composition, more preferably at least 50% by weight, advantageously at least 60% by weight.
- composition may further comprise plastomers.
- composition according to the invention may also contain one or more polymeric components chosen from the category of known bitumen plastomers such as polyethylene PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene copolymer). -vinyl acetate), EMA (polyethylene-methyl acrylate copolymer), copolymers of olefins and unsaturated carboxylic esters EBA (polyethylene-butyl acrylate copolymer), copolymers of ethylene and acrylic acid esters , methacrylic or maleic anhydride, ethylene-propylene copolymers, ABS (acrylonitrile-butadiene-styrene).
- bitumen plastomers such as polyethylene PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene copolymer). -vinyl acetate), EMA (polyethylene-methyl acrylate copolymer), copolymers
- the composition according to the invention comprises at least one plastomer as defined above
- the SBS copolymers represent at least 40% by weight relative to the total mass of all the elastomers and plastomers present in the composition, even more preferably at least 50% by weight.
- the crosslinking agent or vulcanizing agent, comprises a sulfur-containing agent such as sulfur flower, and optionally a binder, the proportions of which are not particularly limited.
- the crosslinking agent consists of sulfur in powder form.
- a binder is present in an amount sufficient to form pellets or granules comprising the sulfur-containing crosslinking agent.
- the vulcanizing agent comprises at least 20% by weight of binder. More preferably, the vulcanizing agent comprises from 20 to 90% by weight of binder and 10 to 80% by weight of the sulfur agent. The vulcanizing agent may further comprise from 0 to 30% by weight of other additives.
- the sulfur-containing agent comprises from 10 to 100% by weight of elemental sulfur and from 0 to 90% by weight of a sulfur-containing compound.
- the sulfur agent may thus comprise a sulfur donor, such as zinc dibutyl dithiocarbamate (ZDBC) or zinc mercaptobenzothiazole (MBT) or a sulfonamide.
- a sulfur donor such as zinc dibutyl dithiocarbamate (ZDBC) or zinc mercaptobenzothiazole (MBT) or a sulfonamide.
- ZDBC zinc dibutyl dithiocarbamate
- MBT zinc mercaptobenzothiazole
- sulfonamide sulfonamide
- the binder is not particularly limited, provided that it allows the granulation of the sulfur-containing agent.
- the binder has a melting point (and / or a softening point) lower than the melting point of the sulfur, to facilitate the implementation of the granule manufacturing process.
- the binder comprises a wax, a hydrocarbon resin, a copolymer of ethylene and an acrylic ester.
- Preferred binders include polyethylene (PE), glycol monostearate (GMS), ethyl vinyl alcohol (EVA) and copolymers of ethylene and ester acrylate.
- a particularly preferred vulcanizing agent is elemental sulfur, and a particularly preferred binder is EVA.
- a particularly preferred binder is EVA.
- sulfur-based granules and a binder are described in WO02 / 34835.
- the olefinic polymer adjuvant is preferably selected from the group consisting of (a) ethylene / glycidyl (meth) acrylate copolymers; (b) ethylene / monomer A / monomer B terpolymers and (c) copolymers resulting from the grafting of a monomer B onto a polymer substrate, (d) mixtures of these copolymers.
- the ethylene / glycidyl (meth) acrylate copolymers are advantageously chosen from random or block copolymers, preferably random copolymers of ethylene and a monomer chosen from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight, preferably from 60% to 95% by weight, more preferably 60% to 90% by weight of ethylene.
- the terpolymers are advantageously chosen from random or sequential terpolymers, preferably random, of ethylene, a monomer A and a monomer B.
- the A monomer is selected from vinyl acetate and alkyl acrylates or methacrylates to C 6.
- Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
- the ethylene / monomer A / monomer B terpolymers comprise from 0.5% to
- the copolymers result from the grafting of a monomer B selected from glycidyl acrylate and glycidyl methacrylate onto a polymer substrate.
- the polymer substrate consists of a polymer chosen from polyethylenes, in particular low density polyethylenes, polypropylenes, statistical or sequential copolymers, preferably random copolymers of ethylene and vinyl acetate, and statistical or block copolymers, preferably statistical copolymers.
- ethylene and alkyl acrylate or methacrylate to C 6 comprising from 40% to 99.7% by weight, preferably from 50% to 99% by weight ethylene.
- Said graft copolymers comprise from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of grafted units derived from monomer B.
- the olefin polymer adjuvant may be a mixture of two or more copolymers selected from categories (a), (b) and (c).
- the olefin polymer adjuvant is preferably selected from terpolymers
- the olefin polymer adjuvant is advantageously chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from the mixtures (d) in which the terpolymers (b) represent at least 50% by mass by weight. relative to the total mass of the mixture, preferably at least 75% by weight, more preferably at least 90% by weight.
- the additive polymer is selected from olefinic random terpolymers of ethylene, a monomer A chosen from acrylates or methacrylates of alkyl to C 6 and a monomer B selected from glycidyl acrylate and glycidyl methacrylate comprising from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and from 0.5% by weight. % to 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
- the amount of olefinic polymer builder is from 0.05% to 2.5% by weight relative to the total weight of the bitumen / polymer composition
- bitumen / polymer composition of the invention in a known manner:
- a) adhesiveness dopes and / or surfactants are generally chosen from alkylamine derivatives, alkyl-polyamine derivatives, alkyl amidopolyamine derivatives and quaternary ammonium salt derivatives, taken alone or as a mixture.
- the amount of adhesiveness dopes and / or surfactants in the bitumen / polymer composition is, for example, between 0.2% and 2% by weight, preferably between 0.5% and 1% by weight. relative to the total mass of the bitumen / polymer composition.
- paraffins having chain lengths of 30 to 120 carbon atoms (C30 to C20 ).
- the 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.
- paraffins are synthetic paraffins resulting from the conversion of biomass and / or natural gas.
- paraffins may also contain a large proportion of so-called "normal" paraffins, that is, straight-chain, unbranched linear paraffins (saturated hydrocarbons).
- the paraffins may comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins and / or branched paraffins.
- the paraffins comprise 85 to 95% of normal paraffins and 5 to 15%) of isoparaffms and / or branched paraffins.
- the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins.
- the paraffins comprise 85 to 95% of normal paraffins and 5 to 15% of isoparaffins.
- the paraffins are paraffins of polymethylene. More particularly, paraffins are synthetic paraffins of polymethylene, especially paraffins resulting from the conversion of synthesis gas by the Fischer-Tropsch process. In the Fischer-Tropsch process, paraffins are obtained by reaction of hydrogen with carbon monoxide on a metal catalyst. Fischer-Tropsch synthesis methods are described for example in the publications EP 1 432 778, EP 1 328 607 or EP 0 199 475.
- the paraffins are Fischer-Tropsch polymethylene paraffins marketed by Sasol, in particular under the Sasobit® trademark.
- 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, 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) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils.
- detergent and / or anti-corrosion additives especially (but not exclusively) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylamines and polyetheramines; imidazolines.
- lubricant additives or anti-wear agent especially (but not exclusively) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocarboxylic acid derivatives and cyclic poly.
- antioxidants for example of the hindered phenol type or amino type of paraphenylene diamine alkylated.
- acid neutralizers 1) acid neutralizers.
- additives for lowering the mixing temperature of asphalts and asphalt those for improving the adhesion of bituminous binders to fillers and aggregates, such as polyisobutylene succinimides.
- n) acids such as polyphosphoric acid or diacids, in particular fatty diacids.
- the additives are used according to the amounts well known to those skilled in the art, depending on the nature of the additive, depending on the bitumen base and the expected properties.
- the bitumen base comprises from 0.1% to 10% by weight, preferably from 0.5% to 5% by weight, more preferably from 0.5% to 2%, 5% o by weight of chemical additive relative to the total mass of the bitumen / polymer composition.
- composition The composition :
- bitumen / polymer composition comprises:
- bitumen / polymer composition comprises:
- bitumen / polymer composition comprises:
- bitumen / polymer composition consists essentially of:
- bitumen / polymer composition consists essentially of:
- bitumen / polymer composition consists essentially of:
- the percentages by weight are calculated with respect to the total mass of said composition.
- bitumen / polymer compositions of the invention may be prepared by any method known to those skilled in the art. Typically these processes include mixing the components and heating the mixture. The bitumen can be heated before mixing. Usually, the bitumen is heated before mixing, and the other components are added to the bitumen without having been previously heated.
- bitumen / polymer composition is prepared by bringing into contact:
- an elastomer composition comprising at least one SBS elastomer
- the percentages by weight are calculated with respect to the total mass of said composition. It operates at temperatures ranging from 100 ° C to 200 ° C, preferably from 150 ° C to 200 ° C, more preferably from 160 ° C to 200 ° C, and with stirring for a period of at least 10 minutes, preferably from 1 hour to 24 hours, more preferably from 1 hour to 10 hours.
- the process of the invention can be carried out by means of agitation producing high shear or low shear agitation.
- the process of the invention may comprise successive sequences with different modes of agitation, for example the process of the invention may comprise at least two successive stirring sequences, a first sequence producing high shear agitation followed by a second sequence producing low shear agitation.
- the process for producing the bitumen / crosslinked polymer composition comprises, for example, the following successive stages: i) the bitumen base is heated to a temperature ranging from 100 ° C. to 250 ° C., preferably from 150 ° C to 220 ° C, more preferably from 160 ° C to 200 ° C,
- the mixture is stirred until a homogeneous mixture is obtained and heated to a temperature ranging from 100 ° C. to 250 ° C., preferably from 150 ° C. to 200 ° C., more preferably from 160 ° C. to 200 ° C. C, for a period of at least 10 minutes, preferably from 1 hour to 24 hours, more preferably from 1 hour to 10 hours,
- the process for producing the crosslinked bitumen / polymer composition comprises, for example, the following successive steps:
- bitumen, the elastomer, the sulfur-containing crosslinking agent and optionally the additives are introduced into a reactor,
- the mixture is stirred at a temperature ranging from 100 ° C to 250 ° C, preferably from 150 ° C to 220 ° C, more preferably from 160 ° C to 200 ° C, for a duration of at least 1 minute preferably between 1 min and 2 hours, more preferably between 1 min and 30 min, then homogenized by passing through a high shear mill, iii) the mixture obtained in stage ii) is then transferred to a maturation tank for a period of at least 30 minutes, preferably 30 minutes to 24 hours, more preferably 1 hour to 10 hours before storage or his job.
- the stirring at high shear and in particular the stirring carried out by passing through a high shear mill, makes it possible to facilitate good dispersion and good distribution of the polymer.
- bitumen / polymer compositions obtained according to the invention are envisaged.
- the bitumen / polymer compositions may be used for the preparation of a bitumen / polymer binder.
- the bitumen / polymer binder according to the invention can be used in combination with aggregates, especially road aggregates.
- the invention aims in particular bituminous mixes as materials for the construction and maintenance of roadway bodies and their coating, as well as for carrying out all road works.
- Asphalt mix means a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers.
- the bituminous mix comprises a bitumen / polymer binder according to the invention, and optionally mineral and / or synthetic fillers and / or recycling costs, preferably chosen from fibers and fines (particles smaller than 0.063 mm in size). , sand (particles of dimensions between 0.063 mm and 2 mm), chippings (particles of dimensions larger than 2 mm, preferably between 2 mm and 4 mm).
- the aggregates are inorganic and / or synthetic aggregates with dimensions greater than 1 mm, preferably between 2 mm and 30 mm, more preferably between 2 mm and 25 mm.
- bitumen / polymer binder according to the invention may advantageously be used to prepare a surface coating, a hot mix, a warm mix, a cold mix, a cold mix or a serious emulsion.
- the invention also relates to asphalts as materials for manufacturing and covering sidewalks.
- asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers.
- An asphalt comprises a bitumen / polymer binder according to the invention and mineral fillers such as fines, sand or chippings and / or synthetic fillers.
- Asphalts are 100% compact and are mainly used to make and cover sidewalks, while asphalt mixes have a compactness of less than 100% and are used to make roads. Unlike asphalt, asphalt is not compacted with a roller when it is put in place.
- bitumen / polymer composition in various industrial applications, in particular for preparing a sealing coating, a membrane or an impregnation layer.
- bituminous compositions As regards the industrial applications of the bituminous compositions according to the invention, mention may be made of the manufacture of waterproofing membranes, anti-noise membranes, insulation membranes, surface coatings, carpet tiles, 'impregnation.
- the subject of the invention is also the use of bitumen / polymer binders, asphalt mixes and cast asphalts according to the invention for the manufacture of road, pavement, sidewalk, road and urban pavement coverings. , floors, waterproofing of buildings or structures, in particular for the manufacture in road application, foundation layers, base layers, bedding layers, surface layers such as connecting layers and / or the wearing courses.
- Figure 1 graph showing the evolution of the ductility of a composition comprising a base B3 and an El or E2 elastomer crosslinked with a sulfur crosslinking agent.
- Figure 2 graph showing the evolution of the ductility of a composition comprising a base B3 and an elastomer El or E2 crosslinked with a sulfur crosslinking agent, after an aging step RTFOT.
- FIG. 3 graph showing the evolution of the TBA variation of a composition comprising a base B3 and an elastomer E1 or E2 crosslinked with a sulfur-containing crosslinking agent.
- Figure 4 graph showing the evolution of the remaining penetrability of a composition comprising a base B3 and an elastomer El or E2 crosslinked with a sulfur crosslinking agent, after an aging step RTFOT.
- bitumens The properties of bitumens are measured using the methods described below:
- TSA Ball and ring softening temperature
- Stability the storage stability is evaluated by measuring the difference in penetrability and the difference in TBA after 3 days of storage at 180 ° C.
- Ductility The ductility is evaluated at 25 ° C. according to ASTM D-13.
- Table 2 Properties of Bases B3, B4 and B5 It can be seen that the Cuban bases have a ductility that meets the standards in force in Cuba. On the other hand, their resistance to aging, evaluated in terms of increasing the TBA and reducing the penetrability remains to be improved.
- the bases B3 and B4 will be used mixed with the base B5 to obtain a penetrability of between 50 and 70 1/10 mm in the presence of an elastomer.
- Elastomer (E) three elastomers in the form of granules were used with the characteristics set out in Table 3 below:
- Mn is the number average molar mass.
- bituminous compositions corresponding to the mixtures detailed in Tables 4 and 5 were prepared according to the protocol below.
- the method comprises the following steps:
- the amounts indicated in the table are percentages by weight relative to the total mass of the composition.
- Figure 3 shows that there is a crosslinked elastomer concentration threshold (close to 3%) to obtain an effect on the control of the increase of softening point after RTFOT. This threshold also corresponds to a marked positive effect on the remaining penetrability (Figure 4).
- compositions were prepared according to the same protocol from bases of different origins, the compositions are detailed in Tables 4 and 5 below.
- the base B 11 has a ductility lower than that referred to by the standards in force in Cuba. It is found that the addition of a crosslinked elastomer in this base makes it possible to increase its ductility, before and after the RTFOT aging, without making it possible to reach the expected specifications.
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Abstract
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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CUP2016000049A CU20160049A7 (es) | 2016-04-14 | 2016-04-14 | Procedimiento de preparacion de una composición bitumen/polímero que presenta propiedades mejoradas |
FR1653332A FR3050210A1 (fr) | 2016-04-15 | 2016-04-15 | Procede de preparation d'une composition bitume / polymere presentant des proprietes ameliorees |
PCT/FR2017/050872 WO2017178753A1 (fr) | 2016-04-14 | 2017-04-11 | Procede de preparation d'une composition bitume / polymere presentant des proprietes ameliorees |
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EP3440130A1 true EP3440130A1 (fr) | 2019-02-13 |
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EP17721775.9A Withdrawn EP3440130A1 (fr) | 2016-04-14 | 2017-04-11 | Procede de preparation d'une composition bitume / polymere presentant des proprietes ameliorees |
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GB8508613D0 (en) | 1985-04-02 | 1985-05-09 | British Petroleum Co Plc | Chemical process |
US5955537A (en) * | 1998-02-13 | 1999-09-21 | The Goodyear Tire & Rubber Company | Continuous polymerization process |
AU9397801A (en) | 2000-10-13 | 2002-04-22 | Bp Exploration Operating | Fischer-tropsch synthesis process |
EP1201717A1 (fr) | 2000-10-24 | 2002-05-02 | ATOFINA Research | Composition vulcanisant le bitume |
WO2003012008A2 (fr) | 2001-07-27 | 2003-02-13 | Sasol Technology (Proprietary) Limited | Production de cire produite par synthese fischer-tropsch |
US7402619B2 (en) * | 2005-03-31 | 2008-07-22 | Kraton Polymers U.S. Llc | Cross-linking compositions for polymer-modified asphalt compositions |
EP2162497B1 (fr) | 2007-05-01 | 2017-09-20 | Kraton Polymers U.S. LLC | Composition de copolymère séquencé et composition de liant hydrocarboné et procédé de préparation associé |
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