Classifications

• • E—FIXED CONSTRUCTIONS
  • E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
  • E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
  • E01C7/00—Coherent pavings made in situ
  • E01C7/08—Coherent pavings made in situ made of road-metal and binders
  • E01C7/18—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders
  • E01C7/26—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre
  • E01C7/265—Coherent pavings made in situ made of road-metal and binders of road-metal and bituminous binders mixed with other materials, e.g. cement, rubber, leather, fibre with rubber or synthetic resin, e.g. with rubber aggregate, with synthetic resin binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
  • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/69—Polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes

Definitions

• the present invention relates to bitumen compositions modified to exhibit improved properties at high temperatures, such as rut resistance, as well as increased resistance to fuels such as kerosene.
• Bitumens find their primary use as a binder for road surfaces or as waterproofing materials; they are also used as shock absorbing underlayers:
• bitumens in the building sector, such as underlayments for slabs, rubber or carpets.
• the mechanical properties of bitumens are very sensitive to temperature. They often become too rigid and fragile at winter temperatures, while they tend to creep at high temperatures (for example in summer).
• bitumens generally have a low resistance to fuels such as kerosene.
• the additives can also be thermoplastic elastomers of the block copolymer type such as SBS (styrene butadiene styrene), SIS (styrene-isoprene-styrene) and SEBS (hydrogenated SBS), EVTA (ethylene-vinyl acetate) and EEA (ethylene ethyl acrylate), as described in the Japanese patents JP-B-5913098, JP-B-6047403, JP-B-15642 and JP-A-63304059.
• Other modifiers for bitumens are thermoplastic epoxies, as described in Japanese patents JP-A-503543, JP-A-6116500 and JP-A-611633.
• bitumen thus modified has an increased resistance to kerosene and other fuels.
• the present invention therefore firstly relates to the use as a modifier for bitumen of a polymer containing free isocyanate functions and resulting from the reaction of:
• the content of free NCO functions of the modifier polymer is between 1 and 10% by weight, in particular from 1 to 5% by weight, relative to the total weight of the modifier.
• the subject of the invention is also a composition of bitumen modified with at least one modifier as defined above.
• the bitumen to be modified can be natural or synthetic; it is generally chosen from bitumens for road surfaces as defined in particular within the meaning of standard NF EN 125 291, bitumens modified by polymers, natural bitumens, semi-blown bitumen, bitumen partially modified with blown bitumen, and all combinations of these bitumens. These bitumens are well known in the state of the art. Their viscosity is not specific, but one could for example consider bitumens having a penetration index between 30 and 220, preferably between 80 and 100.
• Bitumens modified by polymers are for example those defined within the meaning of the document ⁇ Technical Guide: use of modified binders, special bitumens and bitumens with additives in road techniques "published by the Central Laboratory of Bridges and Pavements LCPC CISSN IISI - 1516 15BN 2-7208-7140-4 ".
• the bitumens modified by polymers are advantageously chosen from those modified by styrene-butadiene or styrene-isoprene copolymers and their mixtures and recycled tires.
• composition according to the invention advantageously comprises 0.5 to 30 parts by weight of the modifier, preferably 3 to 10 parts by weight of the modifier, per 100 parts by weight of bitumen.
• the basic constituents (A), (B) and (C) of the modifier according to the invention are described in more detail below, as are other possible ingredients (D), (E) and (F).
• the polyisocyanate (A) is generally chosen from aliphatic, cycloaliphatic and aromatic polyisocyanates well known to those skilled in the art, as well as mixtures of these compounds.
• aliphatic polyisocyanates examples include hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (HMDI), ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate, their derivatives (dimer, trimer, biuret, allophanate) and their mixtures.
• HDI hexamethylene diisocyanate
• HMDI trimethyl hexamethylene diisocyanate
• ethylene diisocyanate ethylene diisocyanate
• ethylidene diisocyanate propylene diisocyanate
• butylene diisocyanate dichlorohexamethylene diisocyanate
• furfurylidene diisocyanate their derivatives (dimer, trimer, biuret, allophanate
• cycloaliphatic polyisocyanates examples include isophorone diisocyanate (IPDI), cyclopentylene-1, 3-diisocyanate, cyclohexylene-1, -diisocyanate, cyclohexylene-1, 2-diisocyanate, their derivatives (dimer , trimer, biuret, allophanate) and their mixtures.
• IPDI isophorone diisocyanate
• cyclopentylene-1 3-diisocyanate
• cyclohexylene-1 -diisocyanate
• cyclohexylene-1 cyclohexylene-1
• 2-diisocyanate their derivatives (dimer , trimer, biuret, allophanate) and their mixtures.
• aromatic polyisocyanates examples include 4,4 "-diphenylmethane diisocyanate (MDI) and its isomers, in particular 2,4'- and 2,2'-diphenylmethane diisocyanate, toluene diisocyanate (TDI) and its isomers, in particular 2,4- and 2,6-toluene diisocyanate, 2, 2-diphenylpropane-4, '-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1 , 4-naphthalene diisocyanate, 1, 5-naphthylene diisocyanate, azobenzene-4, 4 '-diisocyanate, diphenyl sulfone-4, 4' -diisocyanate, 1-chlorobenzene- 2, 4-diisocyanate, 4, 4 ', 4 "-diphenylmethan
• the diisocyanates and more particularly the. MDI and its isomers, TDI and its isomers, HDI, IPDI and their derivatives.
• the polydiene polyol (B) is generally chosen from the hydroxytelechelic conjugated diene oligomers, the copolymers of conjugated diene and a vinyl or acrylic monomer, the hydroxytelechelic oligomers of butadiene epoxidized on the chain and the hydrogenated hydroxytelechelic oligomers of conjugated dienes.
• hydroxytelechelic conjugated diene oligomers which can be obtained by various processes such as radical polymerization of conjugated diene having 4 to 20 carbon atoms in the presence of a polymerization initiator such as hydrogen peroxide or an azo compound such as azobis-2, 2 '[methyl-2, N- ( hydroxy-2-ethyl) propionamide] or the anionic polymerization of conjugated diene having 4 to 20 carbon atoms in the presence of a catalyst such as naphthalene dilithium.
• a polymerization initiator such as hydrogen peroxide or an azo compound such as azobis-2, 2 '[methyl-2, N- ( hydroxy-2-ethyl) propionamide]
• a catalyst such as naphthalene dilithium
• the conjugated diene of the polydiene-polyol is chosen in particular from the group comprising butadiene, isoprene, chloroprene, pentadiene-1, 3 and cyclopentadiene.
• the number-average molar mass of the polyols which can be used can vary from 500 to 15,000 and preferably from 1000 to 3000.
• Copolymers of conjugated diene and of a vinyl or acrylic monomer such as styrene or acrylonitrile are also suitable.
• the OH number of the polydiene polyol (C) expressed in meq / g is advantageously between 0.5 and 5, its viscosity being advantageously between 500 and 100,000 mPa.s at a temperature of 30 ° C.
• polystyrene-polyols By way of illustration of polydien-polyols, mention will be made of polybutadienes with hydroxyl endings marketed by the company "ATOFINA" under the names Poly Bd®R45 HT and Poly Bd®R20 LM.
• the hydroxyl-functional monomer can be, for example, allyl alcohol, N-hydroxymethyl acrylamide, 2-hydroxyethyl (meth) acrylate (HEA or HEMA) or
• (meth) acrylates of diols such as polyethylene glycol (PEG), polyoxypropylene glycol (PPG) or polyoxytetramethylene glycol (PTMG).
• diols such as polyethylene glycol (PEG), polyoxypropylene glycol (PPG) or polyoxytetramethylene glycol (PTMG).
• the unsaturated monomer can also be a carboxylic acid or an anhydride, for example the acid
• the hydroxyl function can also be produced by hydrolysis of a vinyl ester of saturated carboxylic acid such as vinyl acetate or propionate.
• This copolymer (C) is advantageously a terpolymer of ethylene, of an unsaturated carboxylic acid ester and of an unsaturated monomer having at least one hydroxyl function, or an ethylene terpolymer, of a vinyl ester d saturated carboxylic acid and an unsaturated monomer having at least one hydroxyl function.
• alkyl (meth) acrylates the alkyl group having from 1 to 24 carbon atoms, in particular methyl (ethyl), ethyl, n ⁇ butyl, isobutyl, 2-ethylhexyl.
• vinyl esters of saturated carboxylic acids mention may be made of vinyl acetate and vinyl propionate.
• this copolymer (C) mention may be made of the ethylene-vinyl acetate-2-hydroxyethyl acrylate terpolymer.
• the copolymer (C) is obtained by direct copolymerization (as opposed to grafting).
• the copolymer (C) advantageously contains, by weight, 40 to 95% of ethylene, 4 to 40% of comonomer and 1 to 15% of monomer containing at least one hydroxyl function.
• the melt index of the copolymer (C) according to standard ASTM D 1238-73 is advantageously between 1 and 1000 (g / 10 min).
• the copolymer (C) preferably contains from 10 to 45 x 10-- mole of OH per 100 g of copolymer.
• the modifier is prepared in the presence of a monoalcohol ' (D) chain limiter.
• a monoalcohol mention may be made of dodecanol.
• compositions according to the present invention may also contain one or more non-hydroxylated resins (E).
• the preferred resins (E) are aliphatic or aliphatoaromatic (including natural or synthetic terpene resins) and generally do not contain a reactive function with isocyanates.
• resins (E) examples include alphamethylstyrene resin, a polyethylene homo- or copolymer, a copolymer of ethylene and of an unsaturated carboxylic acid ester, a copolymer of ethylene and a vinyl ester of saturated carboxylic acid such as an ethylene-vinyl acetate (EVA) copolymer, a styrene-butadiene-styrene block copolymer (SBS), a copolymer with styrene-isoprene-styrene blocks (SIS) or these hydrogenated block copolymers (SEBS).
• EVA ethylene-vinyl acetate
• SBS styrene-butadiene-styrene block copolymer
• SIS styrene-isoprene-styrene blocks
• SEBS hydrogenated block copolymers
• weakly hydroxylated resins can be used provided that account is taken of the hydroxyl functions which they provide as indicated above and the proportion of alcohol (D) used for the reaction with the excess of polyisocyanate is reduced in proportion.
• compositions according to the present invention may also contain additives (F) such as stabilizers chemically neutral with respect to isocyanates, and waxes.
• additives such as stabilizers chemically neutral with respect to isocyanates, and waxes.
• the proportions of (B) and (C) can be any, advantageously B / C by weight is between 1/100 and 100/1 and preferably between 1/10 and 2/1.
• the possible amount of (D) is such that, by weight, D / (B + C) is between 0 and 5 and preferably between 0 and 2.
• the NCO / OH molar ratio is chosen in order to avoid gelation during synthesis.
• this ratio is between 2 and 30 and preferably between 2 and 5.
• the amount of resin (E) is defined by the mass ratio E / (B + C) ranging from 0 to 10, preferably from 0 to 1.
• the compositions of the invention can be prepared by mixing the various constituents in the molten state.
• the reaction between the copolymer (C) and the polyisocyanate (A) is carried out in the presence of a large molar excess of polyisocyanate in order to avoid any undesired increase in viscosity.
• the excess required depends on the OH functionality of the copolymer (C), of the polydiene-polyol (B) and on the isocyanate functionality and on the reactivity of the polyisocyanate (A) used (a diisocyanate whose two NCO functions have the same reactivity (for example MDI) requires a greater molar excess than a diisocyanate whose two NCO functions do not have the same reactivity (for example TDI)).
• the present invention also relates to the use of the modified bitumen composition as defined above for producing road mixes; membranes, coatings or sealants in the field of building and public works (roofs, tanks, landfills, pipes, electrical connections, bridge decks, carpet underlayments, etc.); expansion joints in the building and public works sector (bridges, airports, roadways, etc.); underbody coverings for automobile bodies; pipe coverings; and shock absorbing underlayers in the transportation and building industries.
• the bitumen composition is used hot (about 150-170 ° C); it is then applied, then compacted.
• the compacting operation requires a low viscosity of the bituminous mixture, in order to ensure the quality of the road surface. It is therefore necessary that the post-crosslinking of the bituminous formulation does not take place too early.
• the post-crosslinking of the modifier of the bituminous composition described in the present invention is carried out by humidity, and can therefore only be carried out after the coating has cooled. Compaction operations are generally carried out between 100 and 140 ° C, no post-crosslinking of the formulation is to be feared during this phase and compaction can be carried out under the best conditions.
• PolyBd polybutadiene with hydroxyl endings
• terpo EVA-HEA ethylene terpolymer - vinyl acetate - 2-hydroxyethyl acrylate
• the bitumen is preheated in an oven to 150 ° C in order to facilitate its implementation. It is then introduced into a melter regulated at 150 ° C. It is poured into a 2 mm thick plate and then cooled to room temperature. Test pieces necessary for characterization are cut from said plate (Reference example 2).
• a quantity of this same bitumen is also preheated to 150 ° C., then introduced into two melters regulated at 150 ° C.
• the additive prepared in Example 1 preheated in an oven at 130 ° C, is introduced in an amount representing 3% and 10% by mass of the bitumen in each of the melters (Examples respectively 3 and 4).
• the contents of each of the melters are then mixed at 150 ° C. using a paddle stirrer (100 rpm) for 5 minutes, then each mixture is poured into a plate 2 mm thick and cools to room temperature. Then, cut test pieces necessary for characterization. All the test pieces (Examples 2 to 4) are placed for 7 days in a climatic chamber at 40 ° C. and 90% residual humidity, in order to allow post-crosslinking by humidity. The test pieces are then stored in a dry atmosphere until evaluation.
• bituminous binders are evaluated according to the specifications proposed by the SHRP program (High Ay Research Program) recognized by the profession. This evaluation made thanks to Bending Beam Rheometer (BBR) tests and mechanical analyzes dynamics (DMA G), makes it possible to determine the plasticity interval (or plasticity interval PI) of the bituminous binder, that is to say its range of temperatures of use, by the data of a high limit temperature T ma ⁇ and an . ' low limit temperature T m - j _ n .
• BBR Bending Beam Rheometer
• DMA G mechanical analyzes dynamics
• the determination of the FRAASS point is still subject to discussion as a parameter for characterizing the behavior at low temperatures of bitumens and modified bitumens.
• the SHRP program suggests instead the use of BBR (see SHRP 1002, SHRP product catalog, 1992).
• This test which consists in imposing on a rod-shaped test piece a constant charge at a series of determined temperatures and measuring the deformation of the test piece as a function of the charging time can be carried out on pure bitumens, special bitumens or bitumens modified by polymers.
• the specification by SHRP indicates that the hardness of the bituminous binder measured by BBR must remain below 300 MPa. In the present example, this limit value was therefore used to determine the lower limit of the temperature of use of the binder.
• the SHRP program specifies that the value G / sin ⁇ must be greater than 1 kPa at the frequency of 10 radians / sec. In the present example, this limit value was therefore used to determine the upper limit of the temperature of use of the binder, temperature directly linked to the creep properties.
• test tubes of the formulations Examples 2, 3 and 4 were immersed in JET Al kerosene (Elf Special Fuels Solaize) for 10 minutes, then dried for 10 minutes. The determination of the loss of mass during this aging makes it possible to illustrate the resistance to kerosene of the various formulations tested.

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  • 2001-01-22 FR FR0100784A patent/FR2819818B1/fr not_active Expired - Fee Related
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