KR20000022071A - Method for preparing bitumen/functionalized elastomer compositions, use thereof in surfacing materials - Google Patents

Abstract

PURPOSE: A method for preparing bitumen/functionalized elastomer compositions is provided which is used in surfacing, coating, and waterproofing materials. CONSTITUTION: Bitumen/functionalized elastomer compositions are prepared by contacting, between 100°C and 230°C and under agitation, an elastomer, a functionalising agent and optionally a peroxide compound. The functionalising agent is a thiolcarboxylic acid polyester or a reaction product of a thiolcarboxylic acid or ester with ethylene sulphide. The functionalized elastomer can also be preformed, then incorporated into the bitumen. The compositions are usable directly or after dilution, for forming bituminous binders to produce surfacing, coating and waterproofing materials.

Description

Process for preparing functionalized elastomer / bitumen composition and application to exterior materials

The present invention relates to a process for the preparation of functionalized elastomer / bitumen compositions. It also relates to the application of the composition prepared by the process of the invention to exterior materials, in particular road pavements, asphalt mixtures, or waterproof exterior materials, and also to a mother liquor that can be used in the process for the preparation of the composition.

U.S. Patent No. 4011184 discloses a process for the preparation of functionalized elastomer / bitumen compositions, one of which is 0.1-25 weight of elastomer, especially bitumen, at a temperature of 100-200 ° C. under stirring. %, In particular 1 to 5% by weight of block copolymers of styrene and conjugated dienes and ethylenically unsaturated carboxylic acids or anhydrides of such acids in amounts of 0.5 to 10% by weight of bitumen and elastomer, eg For example, it is prepared by contacting with maleic anhydride. The contact is then formed in the bitumen directly, by the formation of a hydrogen bond, or by the temperature reversible bridging between the polymer chains of the elastomer and / or between the polymer chain and the bitumen, the addition of a chlorinating agent that can react with the carboxyl group. It is maintained for a time sufficient to produce a functionalized elastomer carrying carboxylic acid or carboxylic anhydride functional groups.

The functionalized elastomer / bitumen composition prepared by the above-mentioned preparation method is an elastomer / bitum prepared by crosslinking an elastomer, in particular a block copolymer of styrene and a conjugated diene (eg butadiene or isoprene) with sulfuric acid in Bitumen. Less gelation occurs than distant compositions. For this reason, functionalized elastomer / bitumen compositions can be prepared that have a high elastomer content and can serve as concentrates. This composition is more economical to manufacture, store and transport than the corresponding composition with low elastomer content, and if dilution is required to form the elastomer / bitumen binder with low content of elastomers commonly used in the manufacture of exterior materials, especially road pavements, It can be easily diluted when used by addition.

However, the functionalized elastomer / bitumen composition prepared by the above-mentioned preparation method disclosed in US Patent No. 4011184 may be used between or after the addition of chloride, between the polymer chain of the elastomer bonded with the bitumen and another polymer chain, and And / or have only a limited level of carboxyl functional groups attached to the polymer chain that can induce crosslinking or bridging between the bitumen. For this reason, the physico-mechanical properties of such compositions, in particular the plasticity range (difference between ring-and-ball softening temperature and prass brittleness point) and the mechanical properties at low temperatures in use, are not completely satisfactory.

French Patent Application No. 9512276, filed October 19, 1995, discloses a process for the production of functionalized elastomeric / bitumen compositions with extended plasticity and improved tensile properties. This method of preparation is comparable to that of US Pat. No. 40111184, which is distinguished by the use of specific functionalizing agents to introduce carboxyl or inducing functional groups which form crosslinks in elastomers and optionally in vitrumen. do. The functionalizing agent is composed of a C ₃ or higher and a thiol carboxylic acid, C ₂ or higher and a thiol carboxylic acid and at least one compound selected from the esters and the disulfide salt of the mono-alcohol.

The inventors now describe the polymers / bituates produced by the process of preparation of the French patent application described above by using polyesters of thiocarboxylic acids and polyols or other functionalizing agents consisting of reaction products of thiocarboxylic acids or esters with ethylene sulfide. It has been found that it is possible to produce polymer / viterman compositions having physicomechanical properties comparable to distant compositions.

It is therefore an object of the present invention to mix the bitumen or bitumen mixture with 0.5-25% by weight of the bitumen, more preferably 1-15% by weight of the elastomer and 0.01-1% or more under stirring at a temperature of 100-230 ° C. A process for preparing a functionalized elastomeric / bitumen composition having a wide plasticity range by contacting with 6% by weight, more preferably 0.05 to 3% by weight, of a functionalizing agent, the functionalizing agent being in a crowd consisting of It is to provide a method characterized by containing at least one compound selected.

(i) formula

Poly (thiolcarboxyl ester) A.

(ii) a material containing an average of 0.1-20, more preferably 0.4-12, (SCH ₂ CH ₂ ) units per molecule of polythiolester A resulting from the reaction of at least one polythiolester A with ethylene sulfide Polythioether B.

(iii) thiol compound D molecules having an average of 0.1-20, more preferably 0.4-12, of (SCH ₂ CH ₂ ) units;

Polythioether E resulting from the reaction of a thiol compound D having ethylene sulfide.

In the above formulas, R is a y-valent hydrocarbon group optionally containing oxygen, and represents a group having a molecular weight of 28 or more and 20,000 or less, more preferably 12,000, and R ₁ represents (t + 2) valent C _{1 to} C ₃₀ , preferably a C ₁ ~C _12, particularly preferably represents a C ₁ ~C ₈ hydrocarbon group, R ₂ is (x + t + 1) valent C ₁ ~C _30, more preferably C ₁ ~C _12, especially preferably a C ₁ ~C ₈ represents a hydrocarbon group, X is a hydrogen atom or ₁ C 1 ~C _12, more preferably represents a C ₁ ~C ₈ hydrocarbon group, R _5, t is 0 or 1, y Is 2-10, More preferably, it is 2-6, Especially preferably, it is an integer of 2-4, x is a number which satisfy | fills x + t <= 3 as number which is 1-3, Preferably it is 1 or 2.

The functionalizing agent is preferably selected from the following materials.

(a) Poly (thiolcarboxylate) A having the formula R- [OOC-R ₃ -SH] _{y '} A _1.

(b) a polythiol ester A ₁ average per molecule from 0.1 to 20, more preferably from 0.4 to 12 of (SCH ₂ CH ₂₎ one or more of a substance containing a unit of a polythiol ester A from the _first reaction of ethylene sulfide liquor Polythioether B produced _1.

(c) Thiol compound D ₁ average 0.1 to 20, more preferably of from 0.4 to 12 per molecule (SCH ₂ CH ₂₎ expression as a material containing a unit of HS-R ₄ - (COOX) a thiol compound having an _{X 1} D Polythioether E ₁ resulting from the reaction of with ethylene sulfide

In the above formulas, R ₃ represents a divalent C ₁ -C ₁₂ , more preferably a C ₁ -C ₈ hydrocarbon group, R ₄ represents a (x + 1) valent C ₁ -C ₁₂ , more preferably C _1- C ₈ hydrocarbon group, R, X, y and x are as described above.

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , where (t + 2) is (x + t + 1) is a divalent, (x + 1) and polyvalent hydrocarbon group, are each linear or branched saturated C _{1 to} C ₁₂ , more preferably C ₁ to C ₈ , particularly preferably C ₁ to C ₆ aliphatic groups, linear or branched unsaturated C _{2 to} C ₁₂ , more preferably C ₂ to C ₈ , especially preferably a C ₂ ~C ₆ aliphatic group, C ₄ ~C _12, may more preferably C ₆ ~C ₈ cycloaliphatic group, or a C ₆ ~C _12, and more preferably an aromatic group.

R of x-valent group may be a high molecular weight hydrocarbon group or a non-polymeric hydrocarbon group. Non-polymeric forms of x, in particular divalent (x = 2), trivalent (x = 3), or tetravalent (x = 4) hydrocarbon groups, are linear or branched saturated or unsaturated C ₂ -C ₃₀ , more preferably Is C ₂ to C ₁₂ , particularly preferably C ₂ to C ₈ aliphatic group, linear or branched unsaturated C _{2 to} C ₁₂ , more preferably C ₂ to C ₈ , particularly preferably C ₂ to C ₆ aliphatic Groups, C _{4 to} C ₁₂ , more preferably C ₆ to C ₈ aromatic groups. The x-valent hydrocarbon group R in polymer form may in particular consist of a divalent (x = 2) polyolefin group having-[P] _n- . Wherein P represents a unit resulting from the polymerization of at least one olefinic C _{2 to} C ₄ monomer, for example ethylene, propylene, butene or butadiene, n is the number of repeats of the units forming the polymer chain of the group It is a number which will have the said molecular weight of 160-20,000, More preferably, the range of 160-12,000. The x-valent hydrocarbon group R may also consist of a divalent (x = 2) oxyalkylene or polyoxyalkylene group having the _formula- [C _h H _2h O] _m -C _h H _2h- . In the above formula, h represents an integer of 2 to 4, m represents a repeating number of the same or different units forming the chain of the group, and the group has a molecular weight in the range of 70 to 20,000, more preferably 70 to 12,000. It is a number. Such groups are in particular (poly) oxyethylene, (poly) oxypropylene or (poly) oxytetramethylene groups.

Examples of the hydrocarbon group R include the following groups.

Here, 1 ≦ m ≦ 250.

These hydrocarbon groups R are each polyols, for example ethylene glycol, glycerol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol, 1,2-pentanediol, penta It is derived by removing OH groups from erytriol, trimethylolpropane, trimethylolhexane or polyethylene glycols having a molecular weight ranging from 106 to 11,062.

Examples of functionalizing agents which can be used in the preparation process of the invention are for example esters of β-mercaptopropionic acid or thioglycolic acid with certain polyols as described above, in particular the formula CH ₃ -CH ₂ -C [CH ₂ OOCCH ₂ SH] ₃ having a trimethylolpropane thioglycolic benzoate, formula CH ₃ -CH ₂ -C [CH ₂ OOCCH ₂ CH ₂ SH] ₃ with trimethyl propane β- mercaptopropionate, formula C [CH ₂ OOCCH ₂ CH ₂ SH ] pentaerythrityl trityl β- mercaptopropionate and formula C [CH ₂ OOCCH ₂ SH] having ₄ Erie trityl thioglycolic benzoate, not only is the average 0.1 to 20, more preferably a sugar molecule having a 0.4~ ₄ Thioethers resulting from the reaction of said esters containing 12 (SCH ₂ CH ₂ ) units with ethylene sulfide, in particular the formula H (SCH ₂ CH ₂ ) _1.1 SCH ₂ COOCH ₃ , H (SCH ₂ CH ₂ ) _1.1 SCH ₂ CH ₂ COOCH ₃ , C [CH ₂ OOCCH ₂ CH ₂ SH] ₄ /0.5 (SCH ₂ CH ₂ ), C [CH ₂ OOCCH ₂ CH ₂ SH] ₄ /3.5 (SCH ₂ CH ₂ ), C [CH ₂ OOCCH ₂ CH ₂ SH] ₄ /3.7 (SCH ₂ CH ₂ ), C [CH ₂ OOCCH ₂ SH] ₄ /1.4 (SCH ₂ CH ₂ ) and thioethers having C [CH ₂ OOCCH ₂ SH] ₄ /2.6 (SCH ₂ CH ₂ ).

The bitumen or bitumen mixture used in the preparation of the functionalized elastomer / bitumen composition has a kinematic viscosity at 100 ° C. of 0.5 × 10 ⁻⁴ m ² / s to 3 × 10 ⁻² m ² / s, preferably Is advantageously selected from a variety of bitumens, from 1 × 10 ⁻⁴ m ² / s to ² × 10 ⁻² m ² / s. This bitumen may be direct distillation or vacuum distillation bitumen, and may be a blone or semi-blown bitumen, a propane or pentane diaspalting residue, a viscosity breakdown residue, furthermore a mixture of some petroleum cuts or bitumen and vacuum distillates or the reactions listed above. It may also be a mixture of two or more of the products. The bitumen or bitumen mixture used in the production process according to the invention has a permeability at 25 ° C. of 5 to 900, preferably 10, as measured according to NF Standard T66004, in addition to the kinematic viscosity being within the ranges previously described. It is preferable that it is -400.

Elastomers used in the production process according to the invention wherein the elastomer functionalized by the sequence containing carboxylic acid or carboxylic ester functional groups in the functionalized elastomer / bitumen composition produced by the production process are at least one elastomer Polymers such as polyisoprene, polynorbornene, polybutadiene, butyl rubber, ethylene / propylene (EP) random copolymers or ethylene / propylene / diene (EPDM) ranum terpolymers. Such elastomers are preferred to be part and the remainder may be composed of one or more polymers or other polymers as described above, and may be comprised entirely of one or more styrenes and conjugated dienes (e.g. butadiene, isoprene, chloroprene, carboxylated). Random or block copolymers of butadiene or carboxylated isoprene, in particular styrene and butadiene with or without random linkage, styrene and isoprene, styrene and chloroprene, styrene and carboxylated butadiene, or styrene and carboxylated isoprene It may be composed of one or more copolymers selected from block copolymers. Copolymers of styrene and conjugated dienes, in particular the copolymers described above, preferably have a styrene content of 5 to 50% by weight. The weight average molecular weight of styrene and conjugated diene, in particular the weight average molecular weight of the copolymer described above, is for example 10,000 to 600,000 Daltons, preferably 30,000 to 400,000 Daltons. Copolymers of styrene and conjugated dienes include styrene and butadiene, styrene and isoprene, styrene and carboxylated butadiene or styrene and carboxylated isoprene having styrene content and weight average molecular weights within the ranges described above. It is preferably selected from coalescing. Styrene in particular having a styrene content and a weight average molecular weight in the range as described above and having a 1,2 double bond derived from butadiene from 12 to 50% by weight, preferably 20 to 40% by weight of the copolymer. Random or block copolymers of and butadiene can be used.

When the incorporation of functionalizing agents into the elastomer and optionally bitumen is required to facilitate the binding of the functional group sequence, the reaction mixture formed from the bitumen or bitumen mixture, the elastomer and the functionalizing agent is free at a temperature of 100 to 230 ° C. Peroxides that generate radicals can be added. The peroxide added in an amount of at least 0%, for example 15%, by weight of the elastomer can in particular be selected from dihydrocarbyl peroxides, for example di-t-butyl peroxide and dicumyl peroxide.

According to the preparation method of the present invention, the bitumen or bitumen mixture is contacted with an elastomer, a functionalizing agent and, if necessary, a peroxide, which produces a reaction product constituting the functionalized elastomer / bitumen composition. An appropriate amount of elastomer in the range as described above is sufficient for a sufficient time under stirring at a temperature of 100 to 230 ° C., more preferably 120 to 190 ° C., generally for several tens to several hours, for example for 30 minutes to 8 hours. By incorporation, a homogeneous mixture of bitumen and elastomer is formed, and then a functionalizing agent is added to the mixture and, if necessary, an appropriate amount of peroxide in the range as described above, and the entire mixture is added to the bitumen or bitumen mixture with elastomer. 100-230 ° C., more preferably equal to or different from the temperature used to incorporate The reaction product constituting the functionalized elastomer / bitumen composition is formed by holding for 10 minutes or more, generally 10 minutes to 5 hours, more preferably 30 minutes to 180 hours, under stirring at a temperature of 0-190 ° C.

Another form of preparation according to the invention is first formed by grafting a functionalizing agent to a selected elastomer to form a functionalized elastomer and then incorporated into the functionalized elastomer bitumen or bitumen mixture. The incorporation step at this time may be performed immediately after the functionalized elastomer is formed or may be performed after storing the functionalized elastomer for some time.

The functionalized elastomer is advantageously prepared by contacting the selected elastomer with the functionalizing agent in an amount of 0.2 to 25% by weight of the elastomer, more preferably 0.5 to 15% by weight. This contacting step may be carried out as is at a temperature of 40 to 250 ° C. or may be carried out in a solvent and / or a diluent.

In order to promote the binding of the sequence to be grafted by the functionalizing agent to the elastomer, a radical initiator may be added to the grafting reaction mixture to generate free radicals at a temperature of 40-250 ° C. for binding if necessary. Such radical initiators are in particular peroxides such as dihydrocarbyl peroxides, for example lauroyl peroxide, bendoyl peroxide, dicumyl peroxide or di-t-butyl peroxide. The amount of radical initiator used is very wide, up to 15% by weight of the elastomer, more preferably from 0.01 to 6% by weight, particularly preferably from 0.05 to 3% by weight.

It is advantageous that the grafting reaction mixture contains from 0.1 to 3.5% by weight of the elastomer, more preferably from 0.1 to 2.5% by weight of one or more antioxidants. In particular, the reaction mixture may contain 0.1 to 1.5%, more preferably 0.1 to 1% by weight of hindered phenol and 0 to 2% by weight, more preferably 0 to 1.5% by weight of dialkylphenyl triphosphite. Can be.

The presence of the hindered phenol or hindered phenol / dialkylphenyl triphosphite blend in the grafting reaction mixture can prevent crosslinking of the elastomer during the grafting process. When both the phenol and dialkylphenyl prephosphite are contained in the grafting reaction mixture, the amount of triphosphite is preferably equal to or greater than the amount of hindered phenol.

Hindered Phenolic Formula

It is preferable to select from the compound which has.

Where R _5, R ₆ and R ₉ are the same or different C ₁ ~C _18, more preferably C ₁ ~C ₁₂ aliphatic hydrocarbon group when, in particular R ₅ and methyl tert- butyl group, R ₆ and R ₉ In the case of hexyl, heptyl, nonyl and octyl groups, k is a number from 0 to 5.

Dialkylphenyl triphosphite is a formula

It is preferable to select from the compound which has.

Wherein R ₇ and R ₈ are the same or different H or C _{1 to} C ₁₈ , more preferably C ₁ to C ₁₂ aliphatic hydrocarbon groups, in particular R ₇ for H, isopropyl and tert-butyl groups, R ₈ If H, tert-butyl, hexyl, heptyl or nonyl group.

As described above, the grafting process may be performed as it is, without any solvent or diluent, or vice versa in a solvent and / or diluent. It is therefore advantageous for the elastomer to comprise 10 to 100% by weight, preferably 15 to 100% by weight of the total weight of the elastomer and the solvent and / or diluent. As the solvent and / or diluent in which the grafting reaction can be performed, any liquid may be used as long as it does not affect the components participating in the grafting reaction, for example, a hydrocarbon, in particular a liquid at a temperature selected for grafting. Or aromatic or aliphatic hydrocarbons such as phosphorus ethylbenzene or hexane or mixtures of ethylbenzene and hexane.

The grafting reaction time is very wide, ranging from several minutes (eg 5 to 10 minutes) to several hours (eg 4 to 5 hours).

If the grafting reaction is carried out in a solvent and / or diluent, the functionalized elastomer resulting from the grafting is diluted by conventional methods, for example by diluting the reaction mixture resulting from grafting and then diluting the diluted mixture with acetone. By precipitation in a precipitate, such as, from the solvent and / or diluent.

100-230 ° C., more preferably in the reaction product produced by contacting the bitumen or bitumen mixture with an elastomer, a functionalizing agent and, if necessary, a peroxide, or by incorporating the functionalized elastomer in the bitumen or bitumen mixture. Under stirring at 190 ° C. activates or strengthens crosslinking between the polymer chains of the elastomer and / or between the polymer chains and the bitumen, thereby improving the physicomechanical properties of the functionalized elastomer / bitumen composition It is also possible, if desired, to add one or more additives that can react with the carboxylic acid or carboxyl ester functional groups involved by bitumen. Such reaction additives are in particular primary or secondary amines, in particular polyamines, alcohols, aminoalcohols, epoxides or metal compounds.

Examples of reaction additives in amine form include, for example, aromatic diamines such as 1,4-diaminobenzene, 2,4-diaminotoluene, diaminonaphthalene, bis (4-aminophenyl) sulfone, bis (4-aminophenyl ) Ether or bis (4-aminophenyl) methane; Aliphatic or cycloaliphatic diamines having the formula H ₂ NR ₁₃ -NH ₂ , wherein R ₁₃ represents a C ₂ -C ₁₂ alkylene or a C ₆ -C ₁₂ cycloalkylene group, for example ethylenediamine, diamino Propane, diaminobutane, diaminohexane, diaminooctane, diaminodecane, diaminododecane, diaminocyclohexane, diaminocyclooctane or diaminocyclododecane; Polyethylenepolyamines or polypropylene pulliamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dipropylenetriamine; Or other fatty amines or polyamines, ie amines or polyamines in which a C ₁₂ to C ₁₈ alkyl or alkenyl group is bonded to the nitrogen atom of the amine group.

Reaction additives in alcohol form include polyols such as diols or triols, in particular the formula HO-R ₁₄ -OH, wherein R ₁₄ is a hydrocarbon group, in particular a C ₂ -C ₁₈ alkylene group, a C ₆ -C ₈ arylene group and C Allyldiol having _{6 to} C ₈ cycloalkylene group]; And polyetherdiol having the formula HO- [CqH ₂ qO] r H, wherein q is a number between 2 and 6, in particular 2 or 3 and r is a number greater than or equal to 2, for example, up to 2-20. There is this. Examples of such polyols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, hexanediol, octanediol, or polyhydroxylated polybutadiene.

Reaction additives in the form of metal compounds are in particular peroxides, oxides, alkoxides, for example methoxides, ethoxides, propoxides, butoxides, in particular tert-butoxides, carboxylates, for example I, II of the Periodic Table of the Elements. , III and Group VIII metals, especially formate and acetate, nitrites, carbonates and bicarbonates of Na, K, Li, Mg, Ca, Cd, Zn, Ba, Al and Fe.

Produced by contacting the reaction product and the bitumen or bitumen mixture constituting the functionalized elastomer / bitumen composition with an elastomer, a functionalizing agent and optionally a peroxide or by incorporating a functionalized elastomer in the bitumen or bitumen mixture The amount of reaction additive (s) to be incorporated into the reaction product may be in the range of 0.01 to 10% by weight, preferably 0.05 to 5% by weight of bitumen present in the reaction product. This amount is preferably from 1 to 4 times the stoichiometric amount at which the functional groups and reaction additive (s) carried by the functionalized elastomer can fully react.

1 to 1 of Bitumen in the mixture formed to form the above-mentioned reaction product constituting the functionalized elastomer / bitumen composition or the reaction product produced by incorporating the functionalized elastomer into the reaction product itself or a bitumen or bitumen mixture. 40 to 100% by weight of a solvent consisting of hydrocarbon oil having an atmospheric pressure deposition range of 100 to 600 ° C, more preferably 150 to 400 ° C, as measured according to ASTM Standard D86-67 in an amount of 2 to 30% by weight. It can be added further under stirring at a temperature of 230 ° C, more preferably 120 to 190 ° C. Petroleum cuts having aromatic properties, petroleum cuts having naphtheno-aromatic properties, petroleum cuts having naphtheno-paraffinic properties, petroleum cuts having paraffinic properties, petroleum or vegetable oils may be particularly preferably used. Hydrocarbon oils are “heavy” enough to not evaporate when added to bitumen, while at the same time exhibiting the same mechanical, elastomeric / bitumen composition produced without any solvent after hot spraying. “Light” enough to be removed as much as possible after being sprayed into the elastomeric / bitumen composition functionalized to restore properties. Solvents may be added to the reaction mixture to produce the reaction products that make up the functionalized elastomeric / bitumen composition at any point in the process of forming this mixture. When a reaction additive is added to the reaction product constituting the functionalized elastomeric / bitumen composition, a solvent may be added to the reaction product before or after the reaction additive is added to the composition. The amount of the solvent added is selected within the above range in consideration of the desired end use.

At any time during the formation of the reaction mixture in the reaction mixture forming the reaction product constituting the functionalized elastomer / bitumen composition, or in the reaction product, or in the bitumen or bitumen mixture, a functionalized elastomer is formed. In the reaction product resulting from incorporation, bitumen and polymers, such as adhesion promoters for the functionalized elastomer / bitumen composition to adhere well to the surface of the mineral, or fillers such as fine talc, carbon black or worn tyios Additives conventionally used in compositions based on the above can be added.

In one production process according to the invention using a hydrocarbon oil as described above as a solvent, the elastomer, the functionalizing agent and, if desired, the peroxide, the reaction mixture produces a reaction product which constitutes the functionalized elastomer / bitumen composition. In order to make up these materials, these materials are incorporated into the bitumen or bitumen mixture in the form of a mother liquor present in the hydrocarbon oil constituting the solvent. In another production method of the invention in which the functionalized elastomer is likewise formed before incorporation into the bitumen or bitumen mixture, the functionalized elastomer is in the form of a mother liquor in which the material is present in the hydrocarbon oil which constitutes the solvent. Can be incorporated.

The mother liquor comprises 10 to 170 ° C. of the components which comprise it: (i) hydrocarbon oils, elastomers, functionalizing agents and, if desired, peroxides, (ii) hydrocarbon oils serving as solvents, and preformed functionalized elastomers. More preferably, when the peroxide is present at a temperature between 40 and 120 ° C., the elastomer in hydrocarbon oil is brought into contact with stirring for a sufficient time at a temperature lower than the decomposition temperature of the material, for example for 30 to 90 minutes, Functionalizing agents and, if desired, peroxides or preformed functionalized elastomers are prepared by obtaining a fully dissolved solution.

Each concentration of (i) elastomer, functionalizing agent and peroxide if desired, or (ii) preformed elastomer in the mother liquor can vary widely, in particular (i) elastomer, functionalizing agent and, if desired, peroxide, or (ii Depends on the nature of the hydrocarbon used to dissolve the functionalized elastomer. The mother liquor comprises (i) 5-40% by weight of hydrocarbon oil, preferably 10-30% by weight of elastomer, 0.05-10% by weight, preferably 0.1% by weight of functionalizing agent, 0-15% by weight of elastomer, preferably May contain 0 to 10% by weight peroxide, or (ii) 5 to 50% by weight of hydrocarbon oil, more preferably 10 to 38% by weight of functionalized elastomer.

In order to prepare the elastomeric / bitumen composition functionalized by the mother liquor method, a mother liquor containing (i) an elastomer, a functionalizing agent and, if desired, a peroxide, or (ii) a functionalized elastomer, is more preferably 100 to 230 ° C. Preferably, the mother liquor is mixed with the bitumen or bitumen composition under stirring at a temperature of 120 to 190 ° C, and then stirred, for example, at a temperature of 100 to 230 ° C, more preferably at 120 to 190 ° C. After addition to the distant mixture, the reaction mixture was stirred at a temperature of from 100 to 230 ° C., more preferably from 120 to 190, for example at a temperature used to prepare a mixture of mother liquor and bitumen or bitumen mixture. Remaining for at least 10 minutes, generally 10 minutes to 90 minutes, forms the reaction product that constitutes the elastomer / bitumen composition.

The amount of mother liquor incorporated into the bitumen or bitumen mixture is selected to produce the desired amount of (i) elastomer, functionalizing agent and, if desired, peroxide, or (ii) functionalized elastomer, based on the bitumen, the amount being It is within the scope described above.

The functionalized elastomer / bitumen composition prepared by the preparation method according to the present invention may be used as it is, and in order to prepare a functionalized elastomer / bitumen binder containing a predetermined concentration of functionalized elastomer, It may be used by diluting with a composition of the present invention having a different characteristic or a bitumen or a bitumen mixture. This predetermined concentration may be equal to the concentration of the functionalized elastomer in the initial functionalized elastomer / bitumen composition (non-dilution composition) or lower (dilution composition). Dilution of the functionalized elastomer / bitumen composition according to the invention with a bitumen or bitumen mixture or a composition of the present invention having different properties may be useful if the functionalized elastomer / bitumen binder should be used immediately after preparation. Immediately after preparation of the composition, if the functionalized elastomer / bitumen binder is to be used after some time after preparation, it may be carried out after some storage.

The bitumen or bitumen mixture used to dilute the functionalized elastomer / bitumen composition according to the present invention may be selected from bitumen as described above suitable for the preparation of the functionalized elastomer / bitumen composition.

Diluting the functionalized elastomer / bitumen composition according to the present invention with a second composition or bitumen or bitumen mixture of the present invention containing a low concentration of functionalized elastomer is a functionalized elastomer / bitumen to be diluted. Dilute to an appropriate concentration under stirring at a temperature of 100-230 ° C., more preferably 120-190 ° C., to form a functionalized elastomer / bitumen binder containing a lower concentration of the functionalized elastomer than that of the composition. It is achieved by contacting a functionalized elastomeric / bitumen composition with a second functionalized elastomeric / bitumen composition or bitumen or bitumen mixture according to the invention.

The functionalized elastomer / bitumen binder composed of the functionalized elastomer / bitumen composition according to the present invention, or the composition according to the present invention so that the functionalized elastomer concentration in the binder is up to the desired level The functionalized elastomer / bitumen compositions or compositions diluted with bitumen or bitumen mixtures may be used for the manufacture of asphalt pavements suitably placed in hot or cold places on road pavements, in particular in the preparation of surface coverings, or in the manufacture of waterproofing coverings. It may be used directly or may be used as an aqueous suspension.

The invention will now be described in more detail by the following non-limiting examples.

Amounts and percentages in this example are by weight unless otherwise indicated.

In addition, the rheological and mechanical properties of the bitumen or functionalized elastomer / bitumen compositions described in this example are as follows.

Permeability measured according to NF standard T66004 and expressed in 1 / 10th of mm

Softening temperature, expressed in degrees Celsius, measured by a ring-and-ball test defined by SF Standard T66008.

Tensile rheological properties measured in accordance with NF Standard T46002, including:

Elongation at break ε _b (%)

Fracture Stress σ _b (daN / ㎠)

-Pfeiffer's number calculated from Equation 1 as follows: PN

In the above Equation 1, "pen" and "RBT" each represent the permeability and ring-and-ball temperature as previously defined, and this value is an index indicating the temperature sensitivity of the composition.

Example 1-9

To evaluate the physicomechanical properties, functionalized elastomeric / bitumen compositions (Examples 4-9) and control elastomeric / bitumen compositions (Examples 1-3) according to the invention were prepared.

The manufacturing process was carried out under the following conditions.

Example 1 (Control)

940 parts of Vitman, which has a permeability value of 74 according to the conditions of NF standard T66004, and 60 parts of a block copolymer of styrene and butadiene having a weight average molecular weight of 250,000 Daltons and a styrene content of 25% as an elastomer at 180 ° C under stirring Placed in the reactor maintained. A homogeneous mass (Control I) that constitutes the elastomer / bitumen composition was then prepared by mixing for 5 hours under stirring at 180 ° C.

Example 2 (Control)

940 parts of bitumen as used in Example 1 and 60 parts of block copolymers of styrene and butadiene as used in Example 1 were placed in a reactor maintained at 180 ° C. under stirring. A homogeneous mass was then obtained by mixing at 180 ° C. for 5 hours with stirring.

To this was added 4 parts of a radical sulfur source consisting of di-t-dodecyl polysulfide, sold under the trademark TPS32 by the company Elf Atochem under stirring at 180 ° C., and the reaction mixture thus formed was then stirred at this temperature for 4 hours. A sulfur-crosslinked elastomer / bitumen composition (Control II) was prepared by holding for a while.

Example 3 (Control)

Sulfur-crosslinking elastomer / bitumen composition (Control III) was prepared using 1.1 parts of sulfur instead of polysulfide in the same manner as described in Example 2.

Example 4 Compositions According to the Invention

Using 3 parts of the functionalizing agent of the present invention composed of pentaerythryl β-mercaptopropionate having the formula C [CH ₂ OOCCH ₂ CH ₂ SH] ₄ instead of polysulfide by the preparation method as described in Example 2 The functionalized elastomer / bitumen composition was prepared.

Example 5 Compositions According to the Invention

Functionalized elastomer / bitumen compositions were prepared in the same manner as described in Example 4. To this composition was added 0.5 parts of an aqueous sodium hydroxide solution containing 50% by weight of anhydrous sodium hydroxide (NaOH) while maintaining 180 ° C under stirring, and the resulting mixture was stirred for 1 hour under stirring at 180 ° C for hydrolysis of the ester functional group. Maintained.

Example 6 (composition according to the present invention)

It was carried out in the same manner as described in Example 4, but with the same amount of the formula CH ₃ -CH ₂ -C [CH ₂ OOCCH ₂ CH ₂ SH] ₃ instead of pentaerythritol β-mercaptopropionate as the functionalizing agent Trimethylolpropane β-mercaptoacetate was used.

Example 7 (composition according to the present invention)

Functionalized elastomers were prepared in the same manner as described in Example 5. To this composition was added 0.5 parts of an aqueous sodium hydroxide solution containing 50% by weight of anhydrous sodium hydroxide (NaOH) while maintaining 180 ° C under stirring, and the resulting mixture was stirred for 1 hour under stirring at 180 ° C for hydrolysis of the ester functional group. Maintained.

Example 8 (composition according to the present invention)

Methyl thioglycolate containing an average of 1.1 (SCH ₂ CH ₂ ) units per molecule of thioglycolate in the same amount, instead of pentaerythritol β-mercaptoacetate as a functionalizing agent, as described in Example 4 The reaction product of and ethyl sulfide was used.

Example 9 (composition according to the present invention)

Functionalized elastomers were prepared in the same manner as described in Example 5. To this composition was added 0.5 parts of an aqueous potassium hydroxide aqueous solution containing 50% by weight of anhydrous potassium hydroxide (KOH) while maintaining 180 ° C under stirring, and the resulting mixture was stirred for 1 hour under stirring at 180 ° C for hydrolysis of the ester functional group. Maintained.

The following rheological properties were measured for each of the control elastomer / bitumen compositions of Examples 1-3 and the functionalized elastomer / bitumen compositions according to the invention of Examples 4-9.

Viscosity at 60 ° C

Permeability at 25 ° C

Ring-and-ball softening temperature

-Number of paper

Tensile flow properties at 5 ° C., ie

Fracture Stress (σ _b )

Elongation at break (ε _b )

The measurement results are shown in Table 1 below.

Example Pure bitterman One 2 3 4 Permeability (0.1 mm) at 25 ° C 74 65 62 58 44 Ring-and-Ball Temperature (℃) 46.7 69 73 75 82.2 Number of paper -1.1 3.4 3.9 4 4.3 Viscosity (Pa.s) at 60 ℃ 180 3400 13,600 14,000 ＞ 50,000 Elongation (ε _b ) 0 130 ＞ 700 ＞ 700 ＞ 700 Stress (daN / ㎠) 0 40 10 11 16 Example 5 6 7 8 99 Permeability (0.1 mm) at 25 ° C 37 49 46 48 45 Ring-and-Ball Temperature (℃) 83 81 83 81 84 Number of paper 3.9 4.4 4.4 4.3 4.5 Viscosity (Pa.s) at 60 ℃ ＞ 50,000 ＞ 50,000 ＞ 50,000 ＞ 50,000 ＞ 50,000 Elongation (ε _b ) ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700 Stress (daN / ㎠) 18 15 19 16 19

In view of the results shown in Table 1 above, the following facts can be clearly seen.

When comparing the results of Examples 2 and 3 with Example 1, the addition of polysulfide or sulfur to the mixture of bitumen and elastomer results in improved consistency due to crosslinking by the sulfur donating effect (ring-and- It is apparent that not only is the increase in the ball temperature), but also the temperature sensitivity is decreased (increased the number of papers), and the elastic properties are also improved (the increase in the stress σ _b at the tensile elongation ε _b maximum elongation).

Comparing the results of Examples 4, 6 and 8 according to the invention with Control Examples 2 and 3, using the functionalizing agents according to the invention instead of TPS or sulfur, grafted functional groups derived from functionalizing agents It is evident that the crosslinking by the sequence significantly improves the consistency (increase in ring-and-ball temperature), viscosity at 60 ° C. and elasticity (increase in stress σ _b at maximum elongation).

In addition, when comparing the results of Examples 4 and 5, 6 and 7, 8 and 9, the addition of a strong base (NaOH or KOH) to the functionalized elastomeric / bitumen composition prepared according to the present invention ensures consistency (ring-end It is clear that the increase in the ball temperature) and the elastic properties (increase in the stress σ _b at maximum elongation) are further improved.

Example 10 (composition according to the present invention)

Functionalized elastomers were prepared in the same manner as described in Example 4. Two blocks of styrene and butadiene having a random linkage consisting of 75% butadiene containing 35% of units having 1,2 double bonds and 25% of styrene containing 10% of block form, with an average molecular weight of 150,000 equal to that of elastomer Copolymers were used.

The functionalized elastomer / biturman composition thus prepared was diluted using bitumen as used in Example 1 at 180 ° C. under stirring to bring the final content of the functionalized elastomer in the dilution composition to 3.5%. The homogenization was carried out by maintaining the dilution composition formed by adding the bitumen at 180 ° C for 1 hour under stirring.

The prepared dilution composition had the following characteristics.

-Penetration at 25 ℃ (1 / 10㎜): 55

Ring and ball temperature (℃): 72

-Number of tapers: 4.2

Stress at 5 ° C. _b (daN / cm): 16

Elongation at 5 ° C. ε _b (%):> 700

Example 11 (composition according to the present invention)

Pentaerythritol in an elastomer consisting of a diblock copolymer of styrene and butadiene containing 25% styrene and 75% butadiene with a weight average molecular weight of 108,800 Daltons and a polydispersity index (weight average molecular weight versus number average molecular weight) of 1.1 Functionalized elastomers were prepared by grafting a functionalizing agent of the invention consisting of β-mercaptopropionate in solution as described above.

This manufacturing process was carried out in a 2 liter stainless steel reactor equipped with a ribbon stirrer and temperature controlled.

Subsequently, 432 parts of a copolymer of styrene and butadiene, 1730 parts of ethylbenzene, and

2.16 parts of antioxidant and 48 parts of functionalizer, which are commercially available from Ciba under the trade name Irganox 1520D, were added into the reactor maintained under nitrogen.

The mixture was gradually heated to 92 ° C. under stirring (rotation speed of the stirrer was 250 rpm). After the copolymer was dissolved, a solution consisting of 67 parts of 30% benzoyl peroxide in water and 20 parts of ethylbenzene was added. After 60 minutes a solution of 0.33 parts of 30% benzoyl peroxide in water and 20 parts of ethylbenzene was added again.

After adding benzoyl peroxide twice, the mixture of the reactor was stirred at 92 ° C. for 180 minutes at the agitation rate described above.

Next, a solution of Irgafos 168 5.18 parts and Ifganox 1520D 4.32 parts of an antioxidant having a formula [tC ₄ H ₉ -C ₆ H ₄ -O] ₃ -P, commercially available from Ciba, was dissolved in 20 parts of ethylbenzene. Was added. 2000 parts of ethylbenzene were added to the polymer solution formed from the grafting to dilute the polymer, and the thus formed dilution solution was added to 40,000 parts of acetone to precipitate the grafted polymer forming the functionalized elastomer. The polymer was then recovered by filtration and then the polymer impregnated in acetone was left under an air stream for about 30 minutes to remove most of the solvent present in the polymer. The polymer was then redissolved in 1200 parts of a mixture of 80% hexane and 20% ethylbenzene containing 14 parts Irgafos 168 and 12 parts Ifganox 1520D. The grafted polymer was placed in a vacuum oven maintained at ambient temperature (about 25 ° C.) to remove the solvent that was still present under vacuum, and then the solvent-free polymer was brought to 60 ° C. for 2 hours in a vacuum oven. It was dried by keeping.

The amount of pentaerythryl β-mercaptopropionate in the grafted elastomer, measured by infrared spectroscopy, was 1.5% by weight.

Analysis of the grafted elastomer by sterile exclusion chromatography showed that the grafted elastomer had a weight average molecular weight of 357,400 daltons and a polydispersity index of 2.8. In the chromatogram there were two distinct individuals, meaning two.

The functionalized elastomer / bitumen composition was prepared by incorporating the functionalized elastomer obtained by the method described above into a bitumen as described in Example 1. The manufacturing method is as follows.

35 parts of functionalized elastomer in the form of mother liquor and 965 parts of bitumen in which 20% by weight of the functionalized elastomer in a hydrocarbon oil having a atmospheric distillation range of 200 to 360 ° C. measured according to ASTM Standard D86-87. It was placed in a reactor maintained at 180 ° C. under stirring. After mixing for 1 hour under stirring at 180 ° C., a homogeneous mass constituting the functionalized elastomer / bitumen composition was obtained. This composition contained 3.6% by weight of functionalized elastomer based on the starting material, Bitumen.

The functionalized elastomer / biturman composition prepared had the following properties. These properties were measured after stabilization by storage at 50 ° C. for 15 days as a 1 mm thick film.

Penetration at 25 ° C (1/10 mm): 90

Ring-and-ball temperature (℃): 60

-Number of paperers: 2.7

-Stress at -10 ° C σ _b (MPa): 0.6

Elongation at -10 ° C ε _b (%):> 700

Example 12 (composition according to the present invention)

Functionalized elastomers were prepared in the same manner as in Example 11, except that ethylene glycol di β-mercaptoacetate was used instead of pentaerythritol β-mercaptopropionate as the functionalizing agent.

The functionalized elastomer contained 1.4 weight percent ethylene glycol dimercaptoacetate with a weight average molecular weight of 465,900 and a polydispersity index of 2.7.

From this grafted elastomer, a functionalized elastomer / bitumen composition containing 3.5% by weight of functionalized elastomer was prepared in the same manner as in Example 11.

The functionalized elastomer / biturman composition prepared had the following properties after stabilization as described in Example 11.

-Penetration at 25 ℃ (1 / 10㎜): 100

Ring and ball temperature (℃): 57

-Number of tapers: 2.4

Stress at −10 ° C. _b (MPa): 0.4

Elongation at -10 ° C ε _b (%):> 700

Example 13 (composition according to the present invention)

Functionalized elastomers were prepared in the same manner as in Example 11, except that di-β-mercaptoacetate of polyethylene glycol having an average molecular weight of 300 g / mol was used as the functionalizing agent.

In this example, 216 parts of a copolymer of styrene and butadiene, 865 parts of ethylbenzene, 1.08 parts of Irganox 1520D, and 24 parts of a functionalizing agent were used.

The mixture was gradually heated to 92 ° C. under stirring (rotator speed of 250 rpm). After the copolymer was dissolved, a solution consisting of 0.34 parts of 30% benzoyl peroxide in water and 20 parts of ethylbenzene was added. After 60 minutes a solution of 0.17 parts of 30% benzoyl peroxide in water and 20 parts of ethylbenzene was added again.

After adding benzoyl peroxide twice, the mixture of the reactor was stirred at 92 ° C. for 180 minutes at the agitation rate described above.

Next, a reaction mixture of 2.59 parts of Irgafos 168 and 2.16 parts of Ifganox 1520D, which is an antioxidant having a commercially available formula [tC ₄ H ₉ -C ₆ H ₄ -O] ₃ -P from Ciba, was dissolved in 20 parts of ethylbenzene was reacted. Was added. 2000 parts of ethylbenzene were added to the polymer solution formed from the grafting to dilute the polymer, and the thus formed dilution solution was added to 4000 parts of acetone to precipitate the grafted polymer forming the functionalized elastomer. The polymer was then recovered by filtration and then the polymer impregnated in acetone was left under an air stream for about 30 minutes to remove most of the solvent present in the polymer. The polymer was then redissolved in 1200 parts of a mixture of 80% hexane and 20% ethylbenzene containing 7 parts Irgafos 168 and 6 parts Ifganox 1520D. The grafted polymer was placed in a vacuum oven maintained at ambient temperature (about 25 ° C.) to remove the solvent that was still present under vacuum, and then the solvent-free polymer was brought to 60 ° C. for 2 hours in a vacuum oven. It was dried by keeping.

The amount of pentaerythryl β-mercaptopropionate in the grafted elastomer, measured by infrared spectroscopy, was 0.6% by weight.

Analysis of the grafted elastomer by sterile exclusion chromatography showed that the grafted elastomer had a weight average molecular weight of 154,600 daltons and a polydispersity index of 1.5. In the chromatogram there were two distinct individuals, meaning two.

From the grafted elastomer, a functionalized elastomer / bitumen composition containing 3.5% functionalized elastomer was prepared. The manufacturing method is as follows.

Vituman 965 parts and 35 parts of the functionalized elastomer as used in Example 1 were placed in a reactor maintained at 180 ° C. under stirring. This was placed in a reactor maintained at 180 ° C. under stirring. After 6 hours of mixing at 180 ° C. under stirring, a homogeneous mass constituting the functionalized elastomer / bitumen composition was obtained.

The functionalized elastomer / biturman composition prepared had the following properties.

Penetration at 25 ° C (1/10 mm): 50

Ring-and-ball temperature (℃): 78

-Number of paperers: 4

-Stress σ _b (daN / cm 2) at 5 ° C .: 14

Elongation at 5 ° C. ε _b (%):> 700

Claims (41)

0.5 to 25% by weight of the bitumen, more preferably 1 to 15% by weight of the elastomer and 0.01% to 6% by weight of the bitumen or the bitumen mixture at a temperature of 100 to 230 ° C. for at least 10 minutes. Is a process for preparing a functionalized elastomer / bitumen composition having a wide plasticity range by contacting with 0.05 to 3% by weight of a functionalizing agent, The functionalizing agent, (i) formula Poly (thiolcarboxyl ester) A having (ii) a substance containing an average of 0.1-20, more preferably 0.4-12, (SCH ₂ CH ₂ ) units per molecule of polythiol ester A resulting from the reaction of at least one polythiol ester A with ethylene sulfide Polythioether B, (iii) thiol compound D molecules having an average of 0.1-20, more preferably 0.4-12, of (SCH ₂ CH ₂ ) units; Containing at least one compound selected from the group consisting of a substance of polythioether E produced from the reaction of thiol compound D having ethylene sulfide with R &lt; 2 &gt; The hydrocarbon group represents a group having a molecular weight of 28 or more and 20,000 or less, more preferably 12,000, R ₁ represents a (t + 2) valence C _{1 to} C ₃₀ , more preferably C ₁ to C ₁₂ , particularly preferably C ₁ Represents a C ₈ hydrocarbon group, R ₂ represents a (x + t + 1) valent C ₁ -C ₃₀ , more preferably C ₁ -C ₁₂ , particularly preferably a C ₁ -C ₈ hydrocarbon group, X is hydrogen the atom or ₁ C 1 ~C _12, more preferably represents a C ₁ ~C ₈ hydrocarbon group, R _5, t is 0 or 1, y is 2 to 10, more preferably 2 to 6, particularly preferred Preferably an integer of 2 to 4, x is 1 to 3, preferably 1 or 2, It is a number which satisfy | fills t <= 3. The method of claim 1, The functionalizing agent, (a) poly (thiolcarboxylate) A ₁ having the formula R— [OOC-R ₃ —SH] _{y ′} ; (b) a polythiol ester A ₁ average per molecule from 0.1 to 20, more preferably from 0.4 to 12 of (SCH ₂ CH ₂₎ one or more of a substance containing a unit of a polythiol ester A from the _first reaction of ethylene sulfide liquor The resulting polythioether B ₁ , (c) Thiol compound D ₁ average 0.1 to 20, more preferably of from 0.4 to 12 per molecule (SCH ₂ CH ₂₎ expression as a material containing a unit of _{HS-R 4 - (COOX)} x with the thiol compounds D ₁ And at least one compound selected from the materials of polythioether E ₁ produced from the reaction of ethylene sulfide with R ₃ is a divalent C ₁ -C ₁₂ , more preferably C ₁ -C _{An 8} hydrocarbon group, R ₄ represents a (x + 1) valent C ₁ -C ₁₂ , more preferably a C ₁ -C ₈ hydrocarbon group, and R, X, y and x are as defined in claim 1 Manufacturing method. The method according to claim 1 or 2, In the formula of the poly (thiolcarboxyl ester) A or A ₁ , y is an integer of 2 to 6, more preferably 2 to 4, and in the formula of the thiol compound D or D ₁ , x is 1 or 2 Manufacturing method characterized in that. The method according to any one of claims 1 to 3, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , where (t + 2) is (x + t + 1) is a divalent, (x + 1) and monovalent hydrocarbon group are linear or branched, respectively Saturated C _{1 to} C ₁₂ , more preferably C ₁ to C ₈ , particularly preferably C ₁ to C ₆ aliphatic groups, linear or branched unsaturated C _{2 to} C ₁₂ , more preferably C ₂ to C ₈ , particularly preferably C ₂ ~C ₆ aliphatic group, C ₄ ~C _12, more preferably C ₆ ~C ₈ cycloaliphatic group, or a C ₆ ~C _12, more preferably, the manufacturing method characterized in that an aromatic group. The method according to any one of claims 1 to 4, In the formula of the functionalizing agent, R is an x-valent group, linear or branched saturated or unsaturated C ₂ -C ₃₀ , more preferably C ₂ -C ₁₂ , particularly preferably C ₂ -C ₈ aliphatic group, C ₄ -C ₁₂ , more preferably a C ₆ -C ₈ cycloaliphatic group or a C ₆ -C ₁₂ , more preferably a C ₆ -C ₈ aromatic group. The method according to any one of claims 1 to 4, In the formula of the functionalizing agent, the x-valent hydrocarbon group R consists of a divalent polyolefin hydrocarbon group having the formula-[P] _n- , wherein P is at least one olefinic C ₂ -C ₄ monomer, in particular ethylene, propylene , Represents a unit resulting from the polymerization of butene or butadiene, n represents the number of repetitions of the units forming the chain of the group, wherein the group has a molecular weight in the range of 160 to 20,000, more preferably 160 to 12,000 Manufacturing method characterized in that. The method according to any one of claims 1 to 4, In the formula of the functionalizing agent, the x-valent hydrocarbon group R consists of a divalent oxyalkylene or polyoxyalkylene group having the _formula- [C _h H _2h O] _m -C _h H _2h- , where h is 2 An integer of -4, m represents a repeating number of the same or different units forming the chain of the group, and the group has a molecular weight in the range of 70 to 20,000, more preferably 70 to 12,000. The group is especially selected from the group consisting of oxyethylene, polyoxyethylene, oxypropylene, polyoxypropylene, oxytetramethylene and polyoxytetramethylene groups. The method according to any one of claims 1 to 7, The functionalizing agent is used in an amount of 0.05 to 3% by weight of bitumen. The method according to any one of claims 1 to 8, The amount of the elastomer is characterized in that 1 to 15% by weight of bitumen. The method according to any one of claims 1 to 9, The bitumen or bitumen mixture has a kinematic viscosity at 100 ° C of 0.5 × 10 ^-4 m ² / s to 3 × 10 ^-2 m ² / s, preferably 1 × 10 ^-4 m ² / s to ² × 10 ^-2 m ² / s. The method of claim 10, The non-tumen or non-tumen mixture has a permeability at 25 ° C. of 5 to 900, preferably 10 to 400 when the kinematic viscosity is measured according to NF standard T66004. The method according to any one of claims 1 to 11, The elastomer is selected from random or block copolymers of styrene and conjugated diene, wherein the conjugated diene is in particular butadiene, isoprene, chloroprene, carboxylated butadiene or carboxylated isoprene. The method of claim 12, The copolymer of styrene and conjugated diene contains 5 to 50% by weight of styrene. The method according to claim 12 or 13, The weight average molecular weight of the copolymer of styrene and conjugated diene is 10,000 to 600,000 Daltons, preferably 30,000 to 400,000 Daltons. The method according to any one of claims 1 to 14, Peroxides, in particular dehydrocarbyl peroxides, which generate free radicals at temperatures of 100 to 230 ° C., are added to reaction mixtures formed from bitumen or bitumen mixtures, elastomers and functionalizing agents, the peroxide being in particular 15 weights of the elastomer A production method characterized by the addition of an amount of less than or equal to%. The method according to any one of claims 1 to 15, In contacting the bitumen or bitumen mixture with an elastomer, a functionalizing agent and, if necessary, peroxide, firstly, the elastomer is added to the bitumen or bitumen mixture at a temperature of 100 to 230 ° C, more preferably 120 to 190 ° C. Under a few minutes to several hours, in particular 30 minutes to 8 hours, to form a homogeneous mixture of bitumen and elastomer, and then a functionalizing agent is added to the mixture and an appropriate amount of peroxide, if necessary, so that the entire mixture is 10 minutes or more, generally 10 minutes to 5 hours, under stirring at a temperature of 100 to 230 ° C., more preferably 120 to 190 ° C., which is the same or different than the temperature used to incorporate the elastomer into the bitumen or bitumen mixture Preferably it is held for 30 minutes to 180 hours to form the reaction product constituting the functionalized elastomer / bitumen composition. A method characterized in that the key. The method according to any one of claims 1 to 14, First, the functionalized elastomer is formed by grafting a functionalizing agent on the selected elastomer, and then the functionalized elastomer is incorporated into a bitumen or bitumen mixture, wherein the incorporation process is followed by the formation of the functionalized elastomer. A process which can be carried out immediately or after storing the functionalized elastomer for some time. The method of claim 17, The process of preparing the functionalized elastomer by grafting is carried out by contacting the selected elastomer with the functionalizing agent in an amount of 0.2 to 25% by weight of the elastomer, more preferably 0.5 to 15% by weight, the contact being 40 It may be carried out as it is at a temperature of ~ 250 ℃ and may be carried out in a solvent and / or diluent. The method of claim 18, Radical initiators which generate free radicals at temperatures of 40 to 250 ° C., the temperature selected for grafting, are added to the grafting reaction mixture, which radical initiators in particular peroxides, for example dihydrocarbyl peroxides, for example For example lauroyl peroxide, benzoyl peroxide, dicumyl peroxide or di-t-butyl peroxide. The method of claim 19, The use amount of the radical initiator is 15% by weight or less, more preferably 0.01 to 6% by weight of the elastomer, particularly preferably 0.05 to 3% by weight. The method according to any one of claims 18 to 20, The grafting reaction mixture further comprises 0.1 to 3.5%, more preferably 0.1 to 2.5% by weight of at least one antioxidant of the elastomer. The method of claim 21, The reaction mixture is an antioxidant of 0.1 to 1.5% by weight of the elastomer, more preferably 0.1 to 1% by weight of hindered phenol and 0 to 2% by weight, more preferably 0 to 1.5% by weight of dialkylphenyl triphosphite A manufacturing method characterized by containing a. The method of claim 22, Wherein said grafting reaction mixture contains both a hindered phenol and a dialkylphenyl triphosphite, wherein the amount of said triphosphite is equal to or greater than the amount of hindered phenol. The method according to any one of claims 16 to 23, The reaction product produced by incorporating the functionalized elastomer into the bitumen or bitumen mixture or the reaction product constituting the functionalized elastomer / bitumen composition is stirred at 100 to 230 ° C, more preferably at 120 to 190 ° C. One or more additives capable of reacting with the carboxylic acid or carboxyl ester functional groups carried by the elastomer and bitumen are added, the reaction additives being in particular primary or secondary amines, in particular polyamines, alcohols, in particular polyols, amino Alcohol, epoxide or metal compound, in particular the process of the metal compounds of Groups I, II, III and VIII of the Periodic Table of the Elements. The method of claim 24, The amount of the reaction additive or the reaction additives incorporated into the reaction product is 0.01 to 10% by weight, preferably 0.05 to 5% by weight of bitumen present in the reaction product. The method according to any one of claims 1 to 25, Resulting from the incorporation of a functionalized elastomer into the reaction mixture formed by contacting the bitumen or bitumen mixture, the elastomer, the functionalizing agent and, if necessary, the peroxide or the reaction product formed by contacting these components or the bitumen or bitumen mixture To the reaction product, a solvent is added to the reaction product under stirring at a temperature of 100 to 230 ° C. in an amount of 1 to 40% by weight, more preferably 2 to 30% by weight, which is measured according to ASTM Standard D86-67. The atmospheric pressure distillation range is 100-600 degreeC, More preferably, it is 150-400 degreeC, The manufacturing method characterized by the above-mentioned. The method of claim 26, Elastomers, functionalizing agents, if desired peroxides or functionalized elastomers are incorporated into bitumen or bitumen mixtures in the form of mother liquors in which these substances are present in the hydrocarbon oil constituting the solvent. The method of claim 27, The mother liquor containing (i) an elastomer, a functionalizing agent and, if desired, a peroxide, or (ii) a functionalized elastomer, is stirred with a bitumen or bitumen mixture under stirring at a temperature of 100-230 ° C, more preferably 120-190 ° C. After mixing, the resultant mixture is then maintained under stirring at a temperature of 100-230 ° C., more preferably 120-190 ° C., for at least 10 minutes, generally 10 minutes to 90 minutes, to obtain the functionalized elastomer / bitumen composition. A method for producing a reaction product comprising forming a reaction product. Use of the functionalized elastomer / bitumen composition prepared by the process according to any one of claims 1 to 28 for the production of the functionalized elastomer / bitumen binder, 29. The binder containing the composition may be used on its own, and any one of claims 1 to 28, wherein the functionalized elastomer / bitumen composition is diluted with a bitumen or bitumen mixture or has different properties. It is used after dilution with another functionalized elastomer / bitumen composition of one of the claims, wherein the binder is used for the production of road pavement in the form of surface covering, for the preparation of asphalt mixtures which are suitably placed in hot or cold places, or of Use that can be used directly in the manufacture and can also be used converted to an aqueous suspension. Hydrocarbon oils having an atmospheric distillation range of 100 to 600 ° C., more preferably 150 to 400 ° C. as measured according to ASTM Standard D86-67, (i) elastomers, functionalizing agents and, if desired, peroxides, or (ii) A mother liquor containing a solution in which a functionalized elastomer formed by grafting an agent to an elastomer is dissolved, in particular, which can be used for the production of the functionalized elastomer / bitumen composition, The functionalizing agent, (i) formula Poly (thiolcarboxyl ester) A having (ii) a substance containing an average of 0.1-20, more preferably 0.4-12, (SCH ₂ CH ₂ ) units per molecule of polythiol ester A resulting from the reaction of at least one polythiol ester A with ethylene sulfide Polythioether B, (iii) thiol compound D molecules having an average of 0.1-20, more preferably 0.4-12, of (SCH ₂ CH ₂ ) units; It is composed of at least one compound selected from the group consisting of a substance of polythioether E produced from the reaction of a thiol compound D having an ethylene sulfide, wherein R is a y-valent hydrocarbon optionally containing oxygen group represents a molecular weight of 28 or more to 20,000 or less, more preferably of 12,000 as a group, R ₁ is a (t + 2) valent C ₁ ~C _30, more preferably C ₁ ~C _12, particularly preferably C ₁ ~ A C ₈ hydrocarbon group, R ₂ represents a (x + t + 1) valent C ₁ -C ₃₀ , more preferably C ₁ -C ₁₂ , particularly preferably a C ₁ -C ₈ hydrocarbon group, X is a hydrogen atom or a monovalent C ₁ ~C _12, more preferably represents a C ₁ ~C ₈ hydrocarbon group, R _5, t is 0 or 1, y is 2 to 10, more preferably 2 to 6, particularly preferred Is an integer of 2 to 4, x is 1 to 3, preferably 1 or 2 as x A mother liquor characterized by being a number satisfying + t ≦ 3. The method of claim 30, The functionalizing agent, (a) poly (thiolcarboxylate) A ₁ having the formula R— [OOC-R ₃ —SH] _{y ′} ; (b) a polythiol ester A ₁ average per molecule from 0.1 to 20, more preferably from 0.4 to 12 of (SCH ₂ CH ₂₎ one or more of a substance containing a unit of a polythiol ester A from the _first reaction of ethylene sulfide liquor The resulting polythioether B ₁ , (c) Thiol compound D ₁ average 0.1 to 20, more preferably of from 0.4 to 12 per molecule (SCH ₂ CH ₂₎ expression as a material containing a unit of HS-R ₄ - (COOX) a thiol compound having an _{X 1} D And at least one compound selected from the materials of polythioether E ₁ produced from the reaction of ethylene sulfide with R ₃ is a divalent C ₁ -C ₁₂ , more preferably C ₁ -C _{An 8} hydrocarbon group, R ₄ represents a (x + 1) valent C ₁ -C ₁₂ , more preferably a C ₁ -C ₈ hydrocarbon group, and R, X, y and x are as defined in claim 1 Mother liquor to do. 32. The method of claim 30 or 31 wherein In the formula of the poly (thiolcarboxyl ester) A or A ₁ , y is an integer of 2 to 6, more preferably 2 to 4, and in the formula of the thiol compound D or D ₁ , x is 1 or 2 Mother liquor characterized in that. The method according to any one of claims 30 to 32, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ , where (t + 2) is (x + t + 1) is a divalent, (x + 1) and monovalent hydrocarbon group are linear or branched, respectively Saturated C _{1 to} C ₁₂ , more preferably C ₁ to C ₈ , particularly preferably C ₁ to C ₆ aliphatic groups, linear or branched unsaturated C _{2 to} C ₁₂ , more preferably C ₂ to C ₈ , particularly preferably C ₂ ~C ₆ aliphatic group, C ₄ ~C _12, more preferably C ₆ ~C ₈ cycloaliphatic group, or a C ₆ ~C _12, more preferably from the mother liquor, characterized in that aromatic group. The method according to any one of claims 30 to 33, wherein In the formula of the functionalizing agent, R is an x-valent group, linear or branched saturated or unsaturated C ₂ -C ₃₀ , more preferably C ₂ -C ₁₂ , particularly preferably C ₂ -C ₈ aliphatic group, C ₄ -C _12, more preferably C ₆ ~C ₈ cycloaliphatic group, or a C ₆ ~C _12, more preferably from the mother liquor, characterized in that a group consisting of C ₆ ~C ₈ aromatic. The method according to any one of claims 30 to 33, wherein In the formula of the functionalizing agent, the x-valent hydrocarbon group R consists of a divalent polyolefin hydrocarbon group having the formula-[P] _n- , wherein P is at least one olefinic C ₂ -C ₄ monomer, in particular ethylene, propylene , Represents a unit resulting from the polymerization of butene or butadiene, n represents the number of repetitions of the units forming the chain of the group, wherein the group has a molecular weight in the range of 160 to 20,000, more preferably 160 to 12,000 Mother liquor characterized in that. The method according to any one of claims 30 to 33, wherein In the formula of the functionalizing agent, the x-valent hydrocarbon group R consists of a divalent oxyalkylene or polyoxyalkylene group having the _formula- [C _h H _2h O] _m -C _h H _2h- , where h is 2 An integer of -4, m represents a repeating number of the same or different units forming the chain of the group, and the group has a molecular weight in the range of 70 to 20,000, more preferably 70 to 12,000. The mother liquid is characterized in that the group is selected in particular from the group consisting of oxyethylene, polyoxyethylene, oxypropylene, polyoxypropylene, oxytetramethylene and polyoxytetramethylene groups. The method according to any one of claims 30 to 36, The elastomer is selected from random or block copolymers of styrene and conjugated dienes, wherein the conjugated dienes are in particular isoprene, chloroprene, butadiene, carboxylated butadiene or carboxylated isoprene, and the copolymer is particularly 5-50% by weight. A mother liquor containing styrene. The method of claim 37, The mother liquor characterized in that the weight average molecular weight of the copolymer of styrene and conjugated diene is 10,000 to 600,000 Daltons, preferably 30,000 to 400,000 Daltons. The method according to any one of claims 30 to 38, The hydrocarbon oil is selected from petroleum cuts having aromatic properties, petroleum cuts having naphtheno-aromatic properties, petroleum cuts having naphtheno-paraffinic properties, petroleum cuts having paraffinic properties, petroleum or vegetable oils Mother liquor characterized in that. The method according to any one of claims 30 to 39, 5-40 wt% elastomer of hydrocarbon oil, 0.05-10 wt% functionalizing agent, 0-15 wt% peroxide of elastomer, more preferably 10-30 wt% elastomer, 0.1-8 wt% functionalizing agent, A mother liquor containing 0 to 10% by weight of peroxide of an elastomer. The method according to any one of claims 30 to 39, A mother liquor characterized by containing 5 to 50% by weight of hydrocarbon oil, more preferably 10 to 38% by weight of functionalized elastomer.