KR20000022070A - Method for preparing bitumen/polymer compositions, use thereof in surfacing materials - Google Patents

Abstract

PURPOSE: A method for preparing bitumen/polymer compositions is provided which has intensified mechanical properties, used in surfacing materials or paving materials for roads. CONSTITUTION: Bitumen/polymer compositions are prepared by contacting, between 100°C and 230°C and under agitation, a bitumen or a mixture of bitumen's with at least one styrene and butadiene copolymer, having a global butadiene content ranging between 50 wt.% and 95 wt.% and a content of butadiene 1,2 double-bond structural units ranging between 12 wt.% and 50 wt.% of the copolymer, and, preferably also a sulfuring coupling agent or a functionalizing agent. The bitumen/polymer compositions are usable, directly or after dilution, for forming bitumen/polymer binders for surfacing materials.

Description

Preparation of Polymer / Vitruant Compositions and Application to Exterior Materials

The present invention relates to a process for preparing polymer / bitumen compositions with enhanced mechanical properties. In particular, the present invention relates to the use of the composition prepared by the process for the preparation of polymers and bitumen binders for use in exterior materials and in particular road pavements, asphalt mixtures, or waterproof exterior materials, and also the preparation of the compositions. A polymer mother liquor that can be used in the present invention.

It is well known that bitumen compositions are used as various surface coatings, in particular as road paving coatings, provided they have a certain level of basic mechanical properties.

These mechanical properties are actually evaluated by measurements by standardized tests, and the most widely used series of mechanical properties is as follows.

A softening point, expressed in degrees Celsius, measured by a ring-and-ball test defined by SF Standard T66008

A brittle point or Fraass point measured according to IP standard 80/53 and expressed in degrees Celsius

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

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

Yield stress σ _y (bar)

Elongation at breakdown stress ε _y (%)

Breaking stress σ _b (bar)

Elongation at break ε _b (%)

From the correlation between the penetrability (abbreviation: pen) and softening point (abbreviation: RBT) of the bitumen composition, also known as Pfeiffer's number (abbreviation: PN), the sensitivity of the bitumen composition to temperature Can be taken as an indicator.

This number is calculated from the following equation.

In Equation 1, A is a slope of a straight line represented by Equation 2 as follows.

The sensitivity to temperature of the bitumen composition decreases as the value of the number of paperers increases, and when the same value decreases as the A value decreases. In the case of a conventional Vitman, the paper value is almost zero.

In general, conventional bitumens do not exhibit all the necessary properties simultaneously, so adding various polymers to these conventional bitumens preferably improves the mechanical properties of bitumen and has improved mechanical properties over bitumen alone. It has long been known that it is possible to form bitumen compositions.

Polymers that can be incorporated into bitumen are generally polyisoprene, butyl rubber, polybutene, polyisobutene, ethylene / vinyl acetate copolymers, polymethacrylate polychloroprene, ethyl / propylene copolymers, ethylene / propylene / dienes Elastomers such as terpolymers or polynorbornene or random or block copolymers of styrene and conjugated dienes.

Among the polymers incorporated in bitumen, in particular, random or block copolymers of styrene and conjugated dienes, especially styrene and butadiene, are effective because they are well soluble in bitumen and provide excellent mechanical and dynamic properties, especially very good viscoelasticity.

In addition, if the polymer incorporated in the bitumen is a copolymer of styrene and a conjugated diene, the stability of this polymer / bitumen composition is determined by its own reaction in which the polymer is chemically coupled to the bitumen by a sulfur-donating coupling agent (FR-A -2,376,188, FR-A-2,429,241, FR-A-2,528,439 and FR-A-0,360,656) or by self-reaction, in which the polymer is functionalized by functionalizing agents in the form of carboxylic acids or esters containing thiol or disulfate groups (France Patent Application No. 9512276, filed October 19, 1995).

The present inventors now use copolymers with butadiene of styrene containing butadiene units having 1,2 double bonds instead of the commonly used styrene / butadiene copolymers, in particular when the polymer / bitumen composition is crosslinked. It has been found that the effect of random or block polymers of styrene and butadiene on improving the mechanical and rheological properties, in particular ductility, temperature sensitivity and tensile mechanical properties, of the containing polymer / bitumen compositions can be further enhanced.

Accordingly, an object of the present invention is to provide a method for preparing a polymer / bitumen composition having improved mechanical properties, wherein the bitumen or bitumen mixture is stirred at a temperature between 100 ° C. and 230 ° C. for at least 10 minutes or more. 0.1 to 30% by weight, preferably 0.3 to 20% by weight, more preferably 0.5 to 10% by weight of units derived from butadiene, containing 50 to 95% by weight, more preferably 60 to 95% by weight. Mixed with a copolymer of styrene and butadiene, wherein the copolymer of styrene and butadiene is a butadiene unit having 1,2 double bonds derived from 12 to 50% by weight of the copolymer, preferably 20 to 40% by weight of butadiene It is to provide a manufacturing method characterized in that it contains.

The copolymer of styrene and butadiene used in the preparation of the polymer / bitumen composition according to the present invention exhibits a linear or star-shaped block polymer structure with or without random linkage, and is derived from the total content of butadiene and 1, It is advantageous that the content of butadiene units having two double bonds is selected from copolymers of styrene and butadiene in the above-described ranges. The weight average molecular weight of the copolymer of styrene and butadiene is on the order of 10,000 to 600,000 daltons, preferably 30,000 to 400,000 daltons.

The copolymers of styrene and butadiene used according to the invention are organometallic compounds of alkali metals, in particular in solutions in a solvent consisting of at least partially a polar solvent, such as tetrahydrofuran or diethyl ether, at temperatures of 0 ° C. or lower. It can be prepared by anionic polymerization of the monomer in the presence of an initiator consisting of an organolithium compound such as alkali lithium, more preferably butyl lithium.

According to a preferred process for the preparation of the polymer / bitumen composition according to the invention, the bitumen or bitumen mixture is mixed with a copolymer of styrene and butadiene under stirring at a temperature of 100-230 ° C. to form a polymer / bitumen composition Further comprising (i) a sulfur-donating coupling agent, (ii) a functionalizing agent taken from a carboxylic acid or ester containing a thiol or disulfate, and (iii) a peroxide generating free radicals at temperatures between 100 ° C and 230 ° C. A crosslinking agent selected from the group consisting of is added.

The bitumen or bitumen mixture used to carry out the production process according to the invention has a kinematic viscosity at 100 ° C. of 0.5 × 10 ⁻⁴ m ² / s to 3 × 10 ⁻² m ² / s, preferably 1 × It is advantageous to be selected from a variety of bitumens from 10 ^-4 m ² / s to ² x 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.

The polymer / bitumen composition according to the present invention, in addition to the copolymer of styrene and butadiene, containing a unit having 1,2 double bonds derived from butadiene as described above, whether crosslinked or not, is styrene and butadiene It may also contain one or more additional polymers different from the copolymer of. Such additional polymer (s) include in particular polyethylene, polypropylene, polybutene, polyisobutene, ethylene / vinyl acetate copolymers, ethylene / propylene copolymers, ethylene / propylene / diene terpolymers, ethylene / alkyl acrylates or methacrylates. Olefin polymers such as copolymers, polymers such as polybutadiene, polyisoprene or polynorbornene or another functionalized olefin polymer with epoxy or COOH groups, for example ethylene / glycidyl acrylate or methacrylate copolymers , Ethylene / alkyl acrylate or methacrylate / glycidyl acrylate or methacrylate terpolymers, in particular ethylene / methyl acrylate / glycidyl methacrylate terpolymer and ethylene / alkyl acrylate or methacrylate / anhydride Maleic acid terpolymers, especially ethylene / butyl acrylic Sites / maleic anhydride a terpolymer.

The amount of additional polymer or polymers to be incorporated into the polymer / bitumen composition is 0.3-20% by weight, preferably 0.5-10% by weight of bitumen in the composition.

The sulfur-donating coupling agent used in the preparation of the crosslinked polymer / bitumen composition may consist of a material selected from the group consisting of sulfur, hydrocarbyl polysulfides, sulfur-donating vulcanization accelerators or mixtures with one another. In particular, the sulfur-donating coupling agent may contain from 0 to 100% by weight of component CA consisting of one or more sulfur-donating vulcanization accelerators and from 100 to 0% by weight of components consisting of one or more vulcanizing agents selected from sulfur and hydrocarbyl polysulfide. Among the substances N containing the substance M at a level of 0.01 to 1, preferably 0.05 to 0.5, in which the weight ratio between the component M containing the component CC and the component CC which is not a sulfur-donating substance and at least one vulcanization accelerator and the component CC is Is selected.

The sulfur which can be used to form one or all of the components of the coupling agent is preferably in the form of flowers, particularly sulfur known by the name alpha sulfur as sulfur crystallized in tetragonal form.

Hydrocarbyl polysulfides that can be used to form the coupling agent in whole or in part form a substance as specified in FR-A- 2,528,439 and R _8- (S) m-(R _9- (S) m-) _W It may be selected from materials having a general formula of R ₁₀ . Wherein R ₈ and R ₁₀ each represent a saturated or unsaturated C _{1 to} C ₂₀ monovalent hydrocarbon group or form a saturated unsaturated C _{1 to} C ₂₀ divalent hydrocarbon group that forms a ring with another atom represented by the formula, and R is ₉ represents a saturated or unsaturated C _{1 to} C ₂₀ divalent hydrocarbon group,-(S) m- group represents a divalent group each formed from m sulfur atoms, the m value may be different from each other and from 1 to 6 As an integer, at least one of the m values is 2 or greater and w represents an integer from 0 to 10.

Preferred poly sulfide is R ₁₁ - has a formula such as R ₁₁ - (S) p. R ₁₁ represents a C ₆ to C ₁₆ alkyl group, for example, a hexyl group, an octyl group, a dodecyl group, a tert-dodecyl group, a hexadecyl group, a nonyl group or a decyl group, and-(S) p- represents p groups. Divalent group formed from the chain arrangement of a sulfur atom is shown, p is an integer of 2-5.

If the coupling agent contains a sulfur-donating vulcanization accelerator, this vulcanization accelerator may be chosen especially from thiuram polysulfides having the formula:

In Formula 1, R ₁₂ may be the same or different and each represent a C _{1 to} C ₁₂ , preferably a C ₁ to C ₈ hydrocarbon group, especially an alkyl group, a cycloalkyl group or an aryl group, or is bonded to the same nitrogen atom. Two R ₁₂ groups are bonded to each other to form a C ₂ to C ₈ divalent hydrocarbon group, u being a number from 2 to 8. Such vulcanization accelerators include, in particular, the following compounds, for example, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, tetraethyl Thiuram disulfide and tetramethylthiuram disulfide and the like.

Further examples of sulfur-donating vulcanization accelerators include disulfides such as alkylphenol sulfides and morpholine disulfides and N, N'-caprolactam disulfides.

Materials that can be used to form component CC of the coupling agent of the form N as a vulcanization accelerator other than a sulfur-donor are in particular mercaptobenzothiazole and its derivatives, in particular benzothiazole metal thiolate and all the benzothiazolesulfens described above. Amide, dithiocarbamate having the following formula (2) and thiuram monosulfide having the following formula (3). Wherein R ₁₂ may be the same or different and is as described above, Y represents a metal and f represents a valence of Y.

Examples of vulcanization accelerators in the form of mercaptobenzothiazoles include benzothiazoleethiolate, benzothiazole disulfide, 2-benzothiazolepentamethylenesulfenamide of metals such as mercaptobenzothiazole, zinc, sodium or copper. , 2-benzothiazole dihydrocarbylsulfenamide (in this case, the hydrocarbyl group is ethyl group, isopropyl group, tert-butyl group or cyclohexyl group), and N-oxydiethylene-2-benzothiazolesulfenamide, etc. have.

Examples of vulcanization accelerators in the form of dithiocarbamate having the formula as described above include, for example, dimethyldithiocarbamate of metals such as copper, zinc, lead, bismuth and selenium, diethyldithiate of metals such as cadmium and zinc. Diamyldithiocarbamate and pentamethylenedithiocarbamate lead or zinc of metals such as orcarbamate, cadmium, zinc and lead.

Examples of thiuram monosulfides having the formula as described above include, for example, dipentamethylenethiuram monosulfide, tetramethylthiuram monosulfide, tetraethylthiuram monosulfide and tetrabutylthiuram monosulfide. Compound.

Other vulcanization accelerators which are not sulfur-donors and do not belong to the above-mentioned class may also be used. Such vulcanization accelerators may also be used. Such vulcanization accelerators include 1,3-diphenylguanidine, di-orthotolylguanidine and zinc oxide, of which zinc oxide is optionally used in the presence of fatty acids.

Details of non-sulfur donors that can be used in the formation of sulfur-donating vulcanization accelerators and sulfur-donating coupling agents are described in European Patent Nos. 0360656 and European Patent No. 0409683, and France, which is incorporated herein by reference. It is described in patent 2528439.

As described above, according to the present method, the coupling agent may be in the form of a single component or in the form of a multicomponent, of which the coupling agent may be formed before use and itself in the mixture in which it is present. Can be formed. The components of the preformed multicomponent or monocomponent coupling agents or the self-formed multicomponent coupling agents can be used, for example, in dissolved state or as a mixture in a solution or suspension with a diluent such as a hydrocarbon compound. have.

The coupling agent provides an amount of free sulfur that represents 0.1-20% by weight, preferably 0.5-10% by weight of the copolymer of styrene and butadiene used in the preparation of the polymer / bitumen composition crosslinked by the coupling agent. It is used in an appropriate amount.

The functionalizing agent used to prepare the functionalized polymer / bitumen composition consists of one or more compounds having the following formula (4).

In Formula 4, Y is a hydrogen atom or a monovalent residue.

R ₁ represents a hydrocarbon group in which (x + z + 1)-is C ₁ to C ₁₂ , preferably C ₁ to C ₈ , and x is H or monovalent C ₁ to C ₁₂ , preferably C ₁ ~C ₈ is a hydrocarbon group (R), z is 0 or 1, x is 1 to 3, preferably an integer of x + y≤3 as 1 or 2.

The functionalizing agent is a compound having at least one formula Y ₁ -SR _3- (COOX) x wherein Y ₁ represents H or a monovalent residue -SR ₃ (COOX) x, and in particular Y ₂ -SR _3- A compound having (COOH) x, wherein Y ₂ represents H or a monovalent residue -SR ₃ (COOH) x, and R ₃ represents a (x + 1) valent C ₁ -C ₁₂ , preferably C ₁ -C ₈ hydrocarbon group, X and x are the same as described above).

In the formula of the functionalizing agent described above, the (x + y + 1) valent hydrocarbon group R ₁ , the (x + 1) valent hydrocarbon group R ₃ and the monovalent hydrocarbon group R are linear or branched saturated C _{1 to} C ₁₂ , respectively, Preferably C ₁ -C ₈ aliphatic group, linear or branched unsaturated C ₂ -C ₁₂ , preferably C ₂ -C ₈ aliphatic group, C ₄ -C ₁₂ , preferably C ₆ -C ₈ cyclo aliphatic group Or C _{6 to} C ₁₂ , preferably a C ₆ to C ₈ aromatic group. Hydrocarbon groups R are linear or branched, C ₁ -C ₁₂ , in particular C ₁ -C ₈ alkyl groups, for example methyl, ethyl, propyl, butyl, isobutyl, isooctyl, 2-ethylhexyl, n-hexyl or n It is preferable that it is an octyl group.

Examples of functionalizing agents are as follows.

(i) a thiol-carboxylic acid, for example, formula HS-CH ₂ thiol acetic acid (thioglycolic acid) with a -COOH, formula HS-CH ₂ -CH ₂ -COOH with a thiol acid, formula HS-CH ₂ -CH Thiol butyrate having ₂ -CH ₂ -COOH,

expression

Mercaptosuccinic acid with

expression

Dimercaptosuccinic acid having, and

expression

Thiosalicylic acid.

(ii) disulfates, for example 2,2'-dithiodiacetic acid having the formula HOOC-CH ₂ -SS-CH ₂ -COOH, formula HOOC-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -COOH 3,3′-dithiodipropionic acid having a formula, HOOC- (CH ₂ ) ₃ -SS (CH ₂ ) 3,4′-dithiodioxane having a _3- COOH formula

2,2′-dithiodisalicylic acid having a moiety.

(iii) esters derived from the above-mentioned acids, in which esters are substituted with functional groups -COOR 'instead of the acid functional group -COOH, wherein R' is a C ₁ -C ₁₂ , more preferably a C ₁ -C ₈ alkyl group, eg For example methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, n-octyl or isooctyl groups.

The functionalizing agent is used in an amount of 0.01 to 6% by weight, in particular 0.05 to 3% by weight, of the bitumen or bitumen mixture used to prepare the functionalized polymer / bitumen composition.

Peroxide, which is a substance that generates free radicals at a temperature of 100 to 200 ° C., may be used alone as a coupling agent to prepare a crosslinked polymer / bitumen composition, and the peroxide may be used to prepare a functionalized polymer / bitumen composition. May be used together with the functionalizing agent. The peroxides used in an amount of at least 0%, for example 15%, by weight of the copolymer of styrene and butadiene may be chosen in particular from dihydrocarbyl peroxide, for example di-t-butyl peroxide and dicumyl peroxide. Can be.

The non-crosslinked or nonfunctionalized polymer / bitumen composition may be a copolymer of styrene and butadiene containing certain amounts of butadiene units having 1,2 double bonds derived from butadiene and, if desired, additional polymers or polymers. At a selected ratio within the range as described above, at a temperature of 100-230 ° C., more preferably 120-190 ° C., under stirring for at least 10 minutes, generally for several tens to several hours, for example for 10 minutes to 8 hours. , In particular by contacting with a bitumen or bitumen mixture for 10 minutes to 5 hours to form a homogeneous mass (polymer / bitumen component) constituting the non-crosslinked and nonfunctionalized polymer / bitumen composition. If a polymer is used together with a copolymer of styrene and butadiene, such as an ethylene / vinyl acetate copolymer or an olefin copolymer by epoxy or COOH groups, the additional polymer may be used before or after the copolymer of styrene and butadiene, or at the same time At any time, it may be brought into contact with a bitumen or bitumen mixture.

If it is desired to prepare a crosslinked polymer / bitumen composition, an uncrosslinked polymer / consisting of a copolymer of styrene and butadiene in the uncrosslinked state and, if desired, an additional polymer or polymers and a bitumen or bitumen mixture The bitumen component is first formed under the above-mentioned conditions, and then, to the uncrosslinked polymer / bitumen component, a suitable amount of sulfur-donating coupling agent or peroxide selected within the above-mentioned range is added, and the entire mixture is not crosslinked. At least 10 minutes, generally 10 minutes to 5 hours, more preferably at a temperature of 100 to 230 ° C., more preferably 120 to 190 ° C., which is equal to or different from the temperature used for the preparation of the non-polymeric / bitumen component. Is maintained for 30 minutes to 3 hours, thereby forming a reaction mass constituting the crosslinked polymer / bitumen component.

If it is desired to prepare a functionalized polymer / bitumen composition, the nonfunctionalized polymer consists of a copolymer of styrene and butadiene in the uncrosslinked state and, if desired, an additional polymer or polymers and a bitumen or bitumen mixture The / bituric component is first formed under the above-mentioned conditions, and then to this unfunctionalized polymer / bituric component is added a suitable amount of functionalizing agent selected in the above-mentioned range and subsequently a peroxide (if used), The mixture is at least 10 minutes under stirring at a temperature of 100-230 ° C., more preferably 120-190 ° C., equal to or different from the temperature used for the preparation of the polymer / bitumen component, generally 10 minutes to 5 hours, more preferably. Preferably, it is maintained for 30 minutes to 3 hours to form the reaction product constituting the functionalized elastomer / bitumen composition.

1-40% by weight, more preferably 2-2, of the non-crosslinked or nonfunctionalized polymer / bitumen composition (polymer / bitumen component) or crosslinked or functionalized polymer composition during formation. A solvent consisting of hydrocarbon oil having an atmospheric distillation range of 100-600 ° C., more preferably 150-400 ° C., as measured according to ASTM Standard D 86-67 in an amount of 30% by weight may be added. 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 restoring the same mechanical properties as polymer / bitumen compositions produced without the use of any solvents after hot spraying. “Light” enough to be removed as much as possible after being sprayed into the polymer / bituric composition. Solvents may be added to bitumen, copolymers of styrene and butadiene, if desired, additional polymers or polymers or mixtures formed from coupling agents or functionalizing agents at any point in the process of forming this mixture, the addition amount of It is selected within the range mentioned above in consideration.

In the reaction product constituting the functionalized polymer / bitumen composition, the crosslinking between the polymer chains of the copolymer and / or between the polymer chain and the bitumen is thereby activated or strengthened and thereby the functionalized polymer / bitumen In order to improve the physicomechanical properties of the composition, it is possible to react with the carboxylic acid or carboxyl ester functional groups involved by copolymers of styrene and butadiene and optionally by the bitumen of the polymerized / bitumen composition functionalized. One or more additives may be added. Such reaction additives are in particular primary or secondary amines, in particular polyamines, alcohols, in particular polyols, acids, in particular polyacids, 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 polypropylenepolyamines 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, from 2 to 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.

Acidic reaction additives are in particular polyacids having the formula HOOC-R ₁₄ -COOH, wherein R ₁₄ is as previously described. Examples of such polyacids include phthalic acid, terephthalic acid, malonic acid, succinic acid, adipic acid, glutaric acid or polycarboxylated polybutadiene.

Reaction additives in the form of metal compounds are in particular peroxides, oxides, alkoxides, for example methoxides, ethoxides, propoxides, butoxides, in particular tert-butoxide, 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.

The amount of reaction additive (s) described above incorporated into the reaction mixture forming the functionalized polymer / bitumen composition is in the range of 0.01 to 10% by weight, in particular 0.05 to 5% by weight, of the bitumen present in the reaction mixture. .

It is also common for polymer / bitumen compositions such as adhesion promoters or fillers such as fine talc, carbon black or frayed tires to adhere the polymer / bitumen composition to the mineral surface well to the mixture forming the polymer / bitumen composition. The additive used as may be added at any time during the formation of the mixture.

In the preparation of polymer / bitumen compositions using hydrocarbon oils as described above as solvents, copolymers of styrene and butadiene, if desired further polymers or polymers and coupling or functionalizing agents, It is incorporated into bitumen or bitumen mixtures in the form of mother liquors present in hydrocarbon oils.

The mother liquor comprises 10 to 170 ° C., more preferably 40 to 120 ° C. components, ie hydrocarbon oils serving as solvents, copolymers of styrene and butadiene, if desired further polymer (s) and coupling or stabilizing agents. It is prepared by contacting with stirring for a sufficient time at a temperature of, for example, 10 minutes to 2 hours to obtain a solution in which the polymer component and the coupling agent or functionalizing agent are completely dissolved in hydrocarbon oil.

The concentrations of copolymers of styrene and butadiene and, if desired, additional polymer (s) and coupling agents or functionalizing agents in the mother liquor can vary widely, in particular depending on the nature of the hydrocarbons used to dissolve these components and coupling agents. Depends. The mother liquor preferably contains a copolymer of styrene and butadiene in an amount of 5 to 40% by weight, in particular 10 to 30% by weight of hydrocarbon oil. If a coupling agent or functionalizing agent is present in the mother liquor, the amount is 0.05 to 15% by weight, more preferably 0.1 to 8% by weight of hydrocarbon oil, and when the peroxide is present in the mother liquor, the amount is styrene and butadiene contained in the mother liquor. It is 0-15 weight% of the copolymer of.

In order to prepare the polymer / bitumen composition by the mother liquor method, a mother liquor containing a copolymer of styrene and butadiene and, if desired, additional polymer (s) and a coupling agent or a functionalizing agent is 100-230 ° C., more preferably 120-120 The mother liquor is mixed with bitumen or a bitumen mixture under stirring at a temperature of 190 ° C, for example at 100-230 ° C, more preferably at 120-190 ° C, and then the mother liquor is added to the bitumen The mixture is stirred at a temperature of 100 to 230 ° C., more preferably 120 to 190 ° C., for example at a temperature used to prepare a mixture of mother liquor and bitumen, for at least 10 minutes, generally for 10 to 2 hours. Retention forms the reaction product that constitutes the polymer / bitumen composition.

The amount of mother liquor mixed with the bitumen or bitumen mixture is selected to produce the desired amount of styrene and butadiene, additional polymers and coupling agents or functionalizing agents on the basis of the bitumen and the amounts are within the ranges described above.

The polymer / bitumen composition prepared according to the process of the invention is selected immediately after preparation, for example from phosphoric acid, sulfuric acid, polyphosphoric acid, sulfonic acid and phosphonic acid as described in French patents 2718747 and 2739863. It can be treated with an acidic adjuvant consisting of one or more acids.

The polymer / bitumen composition prepared by the preparation method according to the present invention may be used as it is, and in order to prepare a polymer / bitumen binder containing a copolymer of a predetermined concentration, the present invention has different characteristics at various concentrations. It may also be used after dilution with a composition or a bitumen mixture. This predetermined concentration may be equal to the concentration of the copolymer of styrene and butadiene in the initial polymer / bitumen composition (non-dilution composition), or may be lower (dilution composition).

Dilution of the polymer / bitumen composition according to the invention with a bitumen or bitumen mixture or a composition of the present invention having different properties may be carried out immediately after preparation of the composition, provided that the polymer / bitumen binder is to be used immediately. If it is necessary to use the polymer / bitumen binder after some time, it may be carried out after some storage. The bitumen or bitumen mixture used to dilute the polymer / bitumen composition according to the invention can be selected from bitumen as described above suitable for the preparation of the polymer / bitumen composition. If necessary, the bitumen or bitumen mixture used for dilution may be pretreated with an acidic aid as described above.

Dilution of the polymer / bitumen composition containing a low concentration of the polymer (copolymer of styrene and butadiene and, if necessary, an additional polymer) with the second composition or bitumen or bitumen mixture of the present invention may be performed by diluting the polymer / bitumen to be diluted. In order to form a polymer / bitumen binder containing a lower concentration of the polymer than in the case of a composition, the polymer / bitum to be diluted at an appropriate concentration under stirring at a temperature of 100-230 ° C, more preferably 120-190 ° C. The distant composition is made by contacting a second polymer / bitumen composition or bitumen or bitumen mixture according to the invention.

A polymer / bitumen binder containing the polymer / bitumen composition according to the present invention, or the composition according to the present invention may be replaced with another composition or bitumen or bitumen mixture of the present invention such that the polymer concentration in the binder is up to the desired level. Diluted compositions can be used directly in the manufacture of road pavements, in particular in surface facings, in the preparation of asphaltous mixtures which are suitably placed in hot or cold places, or in the preparation of waterproofing facings and can be used in the form of aqueous suspensions.

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 polymer / bitumen compositions described in this example, namely, permeability, ring-and-ball softening point, the number of wafers (PN) and the tensile properties (σ _b and ε _b ) are As described.

Example 1-9

In order to evaluate the physicomechanical properties, the polymer / bitumen compositions according to the invention (Examples 5 to 9) as well as the control polymer / bitumen compositions (Examples 1 to 4) were prepared.

The manufacturing process was carried out under the following conditions.

Example 1 (Control)

According to the conditions of NF standard T66004, 950 parts of Vitman with a permeability value of 65, 25% styrene and 75% butadiene containing units having a weight average molecular weight of 120,000 and corresponding 1,2 double bonds 50 parts of a diblock copolymer (copolymer SB1) of styrene and butadiene composed of was put into a reactor maintained at 175 ° C under stirring. The contents in the reactor were then maintained at 175 ° C. for 2.5 hours under stirring to form a homogeneous mass (polymer / bituric component). To this 1.3 parts of sulfur were added and the resulting reaction mixture was kept at 175 ° C. for 3 hours to prepare a crosslinked polymer / bitumen composition.

Example 2 (Control)

To prepare a crosslinked polymer / bitumen composition by the preparation method as described in Example 1, and then to prepare a diluted crosslinked polymer / bitumen composition containing 3.5% of copolymer SB1, the composition was Dilution was carried out using an appropriate amount of bitumen as used in 1.

Example 3 (Control)

The crosslinked polymer / bitumen composition was prepared by the preparation method as described in Example 1. However, instead of the copolymer SB1, a styrene and butadiene having a random connection composed of 85% butadiene containing 8% of units having a weight double molecular weight of 1,20,000 double bonds and 15% of styrene containing 10% of a block form. Diblock copolymers (copolymer SB3) were used.

Example 4 (Control)

To prepare a crosslinked polymer / bitumen composition by the preparation method as described in Example 3, and then to prepare a diluted crosslinked polymer / bitumen composition containing 3.5% of copolymer SB3, the composition was prepared as an example. Dilution was carried out using an appropriate amount of bitumen as used in 1.

Example 5 Compositions According to the Invention

The crosslinked polymer / bitumen composition was prepared in the same manner as described in Example 1. However, instead of copolymer SB1, a diblock copolymer of styrene and butadiene composed of 75% butadiene and 25% styrene containing units having a weight average molecular weight of 120,000 and having 1,2 double bonds in an amount corresponding to 30% of the polymer (SB5) was used.

Example 6 (composition according to the present invention)

To prepare a crosslinked polymer / bitumen composition in the same manner as described in Example 5, and then to prepare a diluted crosslinked polymer / bitumen composition containing 3.5% of copolymer SB5, the composition was prepared in Example 1 Dilution was carried out using a suitable amount of bitumen as used in.

Example 7 (composition according to the present invention)

The crosslinked polymer / bitumen composition was prepared in the same manner as described in Example 1. Styrene and butadiene with a random linkage consisting of 75% butadiene and 25% styrene containing units having a weight average molecular weight of 150,000 instead of copolymer SB1 and having 1,2 double bonds in an amount corresponding to 35% of the polymer. Diblock copolymer (SB7) was used.

Example 8 (composition according to the present invention)

To prepare a crosslinked polymer / bitumen composition in the same manner as described in Example 7, and then to prepare a diluted crosslinked polymer / bitumen composition containing 3.5% of copolymer SB7, the composition was prepared in Example 1 Dilution was carried out using a suitable amount of bitumen as used in.

Example 9 (composition according to the present invention)

Functionalized polymer / bitumen compositions were prepared in the same manner as described in Example 1. Provided a 3,3'-dithiodie having the formula HOOC-CH ₂ -CH ₂ -SS-CH ₂ -CH ₂ -COOH to prepare a functionalized polymer / bitumen composition containing 3.5% copolymer Three parts functionalizing agent consisting of propionic acid and 35 parts diblock copolymer of styrene and butadiene of Example 7 were used.

The following properties were measured for each of the compositions prepared according to the methods of Examples 1-9.

Penetration at 25 ° C

Ring-and-ball softening point (RBT)

-Number of Paper (PN)

-Fracture stress (σ _b ) and elongation at break (ε _b )

The tensile test was carried out at 5 ° C. at a rate of 500 mm / min.

The results obtained are shown in Table 1 below.

The amount of copolymer in the composition is expressed as weight percent relative to the total amount of bitumen and polymer.

Example One 2 3 4 5 6 7 8 9 SB1 (%) 5 3.5 SB3 (%) 5 3.5 SB5 (%) 5 3.5 SB7 (%) 5 3.5 3.5 Pen (1 / 10mm) 52 56 49 53 53 53 45 54 55 RBT (℃) 66.8 56 79.7 64 71.3 64 79.8 64.4 66 PN 2.2 0.6 4.2 1.9 3.2 1.9 4 2.1 2.4 σ _b 13.7 10.8 13.5 11.5 14.1 12 16.5 14.2 14.5 ε _b ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700 ＞ 700

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

When comparing the results of Examples 5 and 6 according to the invention with the corresponding Control Examples 1 and 2, respectively, the same molecular weight and the total amount of butadiene are 1, 2 double bonds in the styrene / butadiene copolymer The higher the butadiene units with, the improved physical properties of the crosslinked polymer / bitumen composition (increased RBT value, permeability value, number of papers)

-Comparing the results of Examples 7 and 8 according to the invention with the corresponding Control Examples 3 and 4, respectively, in the case of relatively high molecular weight styrene / butadiene copolymers, 1,2 double bonds in this copolymer Significantly improved physical properties of crosslinked polymer compositions containing such copolymers when the butadiene units having higher molecular weights exceed the physical properties of the crosslinked polymers / bitumen compositions obtained from very high molecular weight styrene / butadiene copolymers. Let's do it.

Generally in the preparation of crosslinked polymer / bitumen compositions, styrene / butadiene copolymers, in particular styrene / butadiene block copolymers, containing a specific amount of butadiene units having the above mentioned 1,2 double bonds are incorporated into the process of the invention. It can be clearly seen that by using accordingly the consistency and elastic properties of the polymer / viterman composition are substantially improved.

Claims (34)

In the method for producing a polymer / bitumen composition with improved mechanical properties, 50 to 95 weights of units derived from butadiene in an amount of 0.1 to 30% by weight relative to the bitumen or bitumen mixture for at least 10 minutes while stirring the bitumen or bitumen mixture at a temperature between 100 ° C and 230 ° C. And a copolymer of styrene and butadiene containing%, wherein the copolymer of styrene and butadiene contains butadiene units having 1,2 double bonds derived from 12 to 50% by weight of butadiene of the copolymer. Manufacturing method. The method of claim 1, The copolymer of styrene and butadiene contains 20 to 40% by weight of units having 1,2 double bonds derived from butadiene. The method according to claim 1 or 2, The copolymer of styrene and butadiene contains 60 to 95% by weight of the unit derived from butadiene The method according to any one of claims 1 to 3, The copolymer of styrene and butadiene is a production method, characterized in that the linear or star-shaped block copolymer with or without a random link. The method according to any one of claims 1 to 4, The copolymer of styrene and butadiene has a weight average molecular weight of 10,000 to 600,000 Daltons, preferably 30,000 to 400,000 Daltons. The method according to any one of claims 1 to 5, The amount of the copolymer of styrene and butadiene is 0.3 to 20% by weight, more preferably 0.5 to 10% by weight of bitumen or bitumen mixture. The method according to any one of claims 1 to 6, 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 ^The process is characterized in that it is selected from bitumen which is ^-2 m ² / s. The method of claim 7, wherein The bitumen or bitumen mixture is characterized in that the permeability at 25 ℃ 5 to 900, preferably 10 to 400 as measured according to NF standard T66004. The method according to any one of claims 1 to 8, During the preparation of the polymer / bitumen composition, at least one additional polymer which is not a copolymer of styrene and butadiene is incorporated, wherein the total amount of the additional polymer is from 0.3 to 20% by weight of the bitumen in the composition, preferably It is 0.5-10 weight% of the manufacturing method characterized by the above-mentioned. The method according to any one of claims 1 to 9, The bitumen or bitumen mixture is mixed with a copolymer of styrene and butadiene under stirring at a temperature of 100-230 ° C. to form a polymer / bitumen composition, which composition further comprises (i) a sulfur-donating coupling agent, (ii) 1) a crosslinking agent selected from the group consisting of a functionalizing agent taken from a carboxylic acid or ester containing thiol or disulfate and (iii) a peroxide that generates free radicals at temperatures between 100 ° C and 230 ° C. Way. The method of claim 10, The crosslinker is a sulfur-donating coupling agent for preparing a crosslinked polymer / bitumen composition, wherein the sulfur-donating coupling agent is a sulfur, hydrocarbyl polysulfide, sulfur-donating vulcanization accelerator or mixture with one another and And / or a mixture with a vulcanization accelerator which is not a sulfur-donating substance. The method of claim 11, The sulfur-donating coupling agent (i) component CB 100-0 which comprises 0-100% by weight of component CA consisting of at least one sulfur-donating vulcanization accelerator and at least one vulcanizing agent selected from sulfur and hydrocarbyl polysulfide. Substance N containing the substance M at a level in which the weight ratio of the substance M containing the weight% to (ii) at least one vulcanization accelerator other than the sulfur-donating substance and the component CC is 0.01 to 1, preferably 0.05 to 0.5. The manufacturing method characterized in that it is selected from. The method according to any one of claims 10 to 12, The coupling agent is used at a suitable level such that the amount of free sulfur accounts for 0.1-20% by weight, preferably 0.5-10% by weight of the copolymer of styrene and butadiene used to prepare the crosslinked polymer / bitumen composition. Manufacturing method characterized in that. The method of claim 10, The crosslinking agent is a carboxylic acid or ester functionalizing agent containing a thiol or disulfide group for forming the functionalized polymer / bitumen composition, wherein the functionalizing agent is a formula Selected from compounds having Wherein Y is a hydrogen atom or a monovalent moiety R ₁ represents a hydrocarbon group in which (x + z + 1)-is C ₁ to C ₁₂ , preferably C ₁ to C ₈ , x is H or monovalent C ₁ to C ₁₂ , preferably C ₁ ~C ₈ hydrocarbon group (R) and, z is 0 or 1, x is a production method, characterized in that represents an integer of x + y≤3 a they are 1 or 2 to 1 to 3, preferably. The method of claim 14, The functionalizing agent is used in an amount of 0.01 to 6% by weight, more preferably 0.05 to 3% by weight, of the bitumen or bitumen mixture used to prepare the functionalized polymer / bitumen composition. Way. The method of claim 10, The crosslinker is a peroxide that produces free radicals at a temperature of 100-230 ° C. to produce a crosslinked polymer / bitumen composition when used alone, or to prepare a functionalizing polymer / bitumen composition when used with a functionalizing agent. And the peroxide is in particular a dihydrocarbyl peroxide. The method of claim 16, Wherein the peroxide is used in an amount of up to 15% by weight of the copolymer of styrene and butadiene. The method according to any one of claims 1 to 9, The polymer / bitumen composition is prepared at a temperature of 100-230 ° C., more preferably 120-190 ° C., under stirring of a copolymer of styrene and butadiene and, if necessary, an appropriate amount of bitumen or bitumen mixture for the additional polymer or additional polymers. For at least 10 minutes, more preferably 10 minutes to 5 hours. The method according to any one of claims 10 to 17, The crosslinked or functionalized polymer / bitumen component is 100-230 ° C., more preferably with stirring a suitable amount of bitumen or bitumen mixture for the copolymer of styrene and butadiene and, if necessary, additional polymers or additional polymers. At a temperature of 120-190 ° C. for at least 10 minutes, more preferably 10 minutes to 5 hours, and then the desired amount of coupling agent to the reaction product comprising the uncrosslinked polymer / bitumen component thus prepared Or a functionalizing agent is added and the resulting mixture is stirred at a temperature of 100-230 ° C., more preferably 120-190 ° C. for at least 10 minutes, more preferably 10 minutes to 5 hours, particularly preferably 10 Produced by forming a reaction mass constituting the crosslinked or functionalized polymer / bitumen component by holding for minutes to 3 hours. Method. The method according to any one of claims 1 to 19, 1-40% by weight of solvent, more preferably 2-30% by weight of solvent, is added to the polymer / bitumen composition during the production process. The method of claim 20, The solvent consists of hydrocarbon oil having an atmospheric distillation range of 100-600 ° C., more preferably 150-400 ° C. as measured in accordance with ASTM Standard D86-67, the hydrocarbon oil having a particularly aromatic character, petroleum cut, naphtheno A petroleum cut having aromatic properties, petroleum cut having naphtheno-paraffinic properties, petroleum cut having paraffinic properties, petroleum or vegetable oil. The method of claim 21, Copolymers of styrene and butadiene and, if necessary, further polymers or additional polymers and coupling agents or functionalizing agents are incorporated in the bitumen or bitumen mixture in the form of a mother liquor in which these substances are present in the hydrocarbon oil constituting the solvent. Manufacturing method. The method of claim 22, The mother liquor is mixed with a bitumen or bitumen mixture at a temperature of 100 to 230 ° C., more preferably 120 to 190 ° C. under stirring, and the mixture thus formed is 100 to 230 ° C., more preferably 120 to 190 ° C. A process for producing a polymer / bitumen composition by maintaining it under stirring at a temperature of at least 10 minutes, in particular for 10 minutes to 2 hours. The method according to claim 14 or 15, During the manufacturing process, at least one additive is added to the polymer / bitumen composition which can react with the functional group of the functionalized copolymer of styrene and butadiene, the reaction additive being in particular primary or secondary amines, in particular polyamines, alcohols, In particular polyols, acids, in particular polyacids or metal compounds, in particular 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 mixture forming the polymer / bitumen composition is 0.01 to 10% by weight, preferably 0.05 to 5% by weight of the bitumen or bitumen mixture. As a use of the polymer / bitumen composition obtained by any one of claims 1 to 25 for the production of a polymer / bitumen binder, The binder containing the composition may be used on its own, and the polymer / bitumen composition is diluted with a bitumen or bitumen mixture, or the polymer content is low, according to any one of claims 1 to 25. It is used after dilution with another polymer / bitumen composition of the binder, the binder can be used directly in the production of road pavement in the form of surface covering, the production of asphalt mixtures properly placed in a hot or cold place, or the production of waterproof packaging Or may be used as an aqueous suspension. (i) a styrene containing from 50 to 95% by weight of a hydrocarbon oil having an atmospheric distillation range of 100 to 600 ° C, more preferably 150 to 400 ° C, and (ii) butadiene, as measured according to ASTM Standard D86-87. In the mother liquor containing a copolymer of and butadiene, which can be particularly used in the preparation of the polymer / bitumen composition, The copolymer of styrene and butadiene contains a unit having 1,2 double bonds derived from 12 to 20% by weight of butadiene of the copolymer. The method of claim 27, The copolymer of styrene and butadiene contains 20 to 40% by weight of units having 1,2 double bonds derived from butadiene. The method of claim 27 or 28, The copolymer of styrene and butadiene contains 60 to 95% by weight of units derived from butadiene. The method according to any one of claims 27 to 29, The copolymer of styrene and butadiene is a mother liquor, characterized in that the linear or star block copolymer having a random connection. The method according to any one of claims 27 to 30, The copolymer of styrene and butadiene has a weight average molecular weight of 10,000 to 600,000 Daltons, preferably 30,000 to 400,000 Daltons. The method according to any one of claims 27 to 31, The amount of the copolymer of styrene and butadiene is 5 to 40% by weight, more preferably 10 to 30% by weight of the hydrocarbon oil. The method according to any one of claims 27 to 32, The mother liquor is selected from (i) a sulfur-donating coupling agent, (ii) a functionalizing agent taken from a carboxylic acid or ester containing a thiol or disulfate group and (iii) a peroxide that generates free radicals at temperatures between 100 and 230 ° C. The mother liquid further containing the crosslinking agent comprised from the 1 or more types of compound which become. The method of claim 33, wherein A mother liquor containing 0.05 to 15% by weight of hydrocarbon oil, more preferably 0.1 to 8% by weight of sulfur-donating coupling agent or functionalizing agent and 0 to 15% by weight of peroxide of the copolymer.