DK176109B1 - Process for the preparation of bitumen-polymer preparations, as well as obtained by the process - Google Patents

Description

DK 176109 B1

The present invention relates to a process for the preparation of bitumen polymer compositions, and to such compositions obtained by the process. The invention further relates to the use of the compositions obtained in the manufacture of coatings, in particular street and road coatings, envelopes or even denser coatings, and the invention also relates to a polymeric stock solution useful in the manufacture of said compositions.

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It is known to use bituminous compositions for coating different surfaces, especially as surface layers applied to streets and roads, provided that such compositions possess a certain number of significant mechanical quality properties.

These mechanical quality properties are assessed in practice by determining, during the use of normalized tests, a series of mechanical characteristics, among which the most frequently used are the following: - softening point expressed in ° C and determined by so-called ball and ring test, as is defined by the French standard NFT 66 008, 25 j, - a brittleness point or a so-called Fraass point expressed in ° C and determined according to the standard IP 80/53, - penetration expressed in 1/10 mm and determined in accordance with \ 30 accord with the French standard NFT 66 004, 2 DK 176109 B1 - rheological characteristics of features determined in accordance with the French norm NFT 46 002 and comprising the following sizes:> 5 threshold value ts in bar extension at threshold value es in% breaking strength rr in bar fracture elongation sr in%.

The conventional bitumens generally do not at the same time exhibit the total amount of required quality properties, and it has long been known that the addition of various polymers to these conventional bitumens makes it possible to advantageously modify the mechanical properties thereof and to form bitumen. polymer compositions possessing improved mechanical quality properties over the properties of the bitumen alone.

The polymers suitable to be added to the bitumen are most frequently elastomers such as polyisoprene, butyl rubber, polybutene, polyisobutene, ethylene / vinyl acetate copolymers, polymethacrylate, polychloroprene, ethylene / propylene / diene terpolymer (EPDM), polynorbornene or static copolymers or sequence copolymers of styrene and of a conjugated diene. )

Among the polymers added to the bitumen, the statistical copolymers or sequence copolymers of styrene 30 and of a conjugated diene, particularly of styrene and of butadiene or styrene and of isoprene, are particularly effective, in particular: DK 176109 B1 3 which dissolve very readily in the bitumen and give them excellent mechanical and dynamic properties, especially very good viscoelasticity properties.

It is further understood that the stability of bitumen polymer compositions can be improved by chemically coupling the polymer with bitumen, this enhancement further providing an extension of the scope of the bitumen polymer compositions.

10

Bitumen polymer compositions can be prepared in which a statistical copolymer or a sequence copolymer of styrene and of a conjugated diene such as butadiene or isoprene is coupled to bitumen, using the methods described in French Patent Nos. A-2376188, A-2429241 and A-2528439. In these methods, the copolymer in question and a source of sulfur are incorporated into bitumen, operating between 130 ° C and 230 ° C and with stirring, keeping the mixture thus formed under stirring and at a temperature between 130 ° C and 25 ° C. 200 ° C for at least 15 minutes.

The source of sulfur consists of chemically unbound sulfur (French Patent No. A-2376188 and French Patent No. A-2429241) or of a polysulfide (French Patent No. A-2528439), and the incorporation of the copolymer and of the source of sulfur to bitumen is carried out either (by direct addition of these constituents to bitumen (French Patent Nos. A-2376188 and A-2528439) or also by first preparing a stock solution 30 of the copolymer and of the source of sulfur in a hydrocarbon oil to which this stock solution is added to 4 DK 176109 B1 bitumen (French Patent Nos. A-2429241 and A-2528439).

As can be seen from FR-A-2,429,241 (page 4, lines 10-12) or the corresponding GB-A-2,025,986 (page '2, line SOSI), the effect of sulfur can be enhanced by the presence of vulcanization accelerators such as mercapto -2-benzothiazole or o-tolylguanidine or activators such as zinc stearate, that is, products that are not sulfur donors.

It has now been found that the mechanical characteristics and stability of bitumen polymer compositions by which a block copolymer of styrene or of a conjugated diene, especially butadiene and isoprene, with bitumen can be significantly improved further effect of a coupling agent that plays the role of sulfur donor, if that coupling agent included at least one vulcanization accelerator, which directly played the role of 20 sulfur donor, or which complemented the effect of such. The static mechanical characteristics, especially determined by tensile tests, are particularly improved at low temperature and are retained on a large scale after simulated aging. This preservation of characteristics constitutes a measure 25 for the duration of the quality of these bitumen polymer compositions, which are most frequently produced in larger quantities and thus stored at high temperature for a duration shorter or longer before being used.

European Patent Application No. 88401558 of 21.06.1988 (Publication No. 0299820 of 18.01.1989) relates to a vulcanizing composition which can be used to vulcanize an elastomer, in particular a three-block copolymer styrene / butadiene / styrene mixed with bitumen. This composition comprises 0.5 to 3 parts by weight of mercaptobenzothiazole, 0.5 to 5 parts by weight of tetramethylthiuram disulphide, 3 to 5 parts by weight

ZnO, 1 to 3 parts by weight of stearic acid, 1 to 4 parts by weight of antioxidant and 1 to 5 parts by weight of a vulcanizing agent composed of 0 to 100% sulfur plum, 0 to 75% of a sulfur donor selected from thiurams and dithiomorpholines and 10 to 50% of a sulfenamide, the weight ratio of sulfenamide to sulfur donor being 1: 3 to 1: 1.

International patent application PCT / BE89 / 00026 of 09.06.1989 (publication no. WO89 / 12079 of 14.12.1989) and European patent application no. 89907645, which has led to publication no. 0424420, relate to a method for producing. position of bitumen / rubber products, at a temperature between 140 ° C and 200 ° C. contacting bitumen with a penetration of between 20 and 320, a cautious ill polymer, e.g. a block polymer of styrene and butadiene or isoprene, a coupling agent in the form of a sulfur derivative of the disulfide or dithiocarbamate type and elemental sulfur, in a weight ratio sulfur derivative: elemental sulfur of between 40:60 and 80:20 and optionally an alkaline compound, which is soluble in bitumen.

The present invention relates to a process for the preparation of bitumen polymer compositions, whereby at a temperature between 100 ° C and 230 ° C, a mixture of bitumen is prepared with a block copolymer of styrene and of a conjugated diene used in a an amount of 0.5-15% by weight 6 based on the bitumen content and a coupling agent comprising a sulfur donor compound, thereby maintaining the mixture thus obtained in said temperature range and with stirring for a period of at least 10 minutes, which The method is characterized in that the incoming coupling agent is selected from: the products M, which comprise 1-100% by weight of a component A consisting of one or more sulfur donor vulcanization accelerators and 99-0% of one. component B consisting of one or more vulcanizing agents selected from elemental sulfur and hydrocarbon polysulfides; and in that the coupling agent described is used in an amount appropriate to introduce such amount of sulfur as to make up 0.5-10% by weight, especially 1-8% by weight, of the bitumen-polymer polymer for the preparation. the copolymers used provided that no alkaline compound soluble in bitumen is added to the reactive medium when the coupling agent consists of a mixture of a sulfur-donor vulcanization accelerator of the sulfur-type elemental sulfur in a weight ratio of sulfur to medium 40:60 and 80:20.

In particular, the products M from which one can select the coupling agent comprise expressed as weight% 10-100% of component A and 90-0% of component B.

25

The sulfur donor vulcanization accelerators useful for the formation of component A of product M may be selected especially from thiuram polysulfides of the general formula: 30 7 DK 176109 B1

R S S R

\ II II /

N - C (S) - C - N

/ x \

5 R R

wherein the substituents labeled R, which may be identical or different, each represent a C 1 -C 12 hydrocarbon group, preferably a C 1 -C 8 hydrocarbon group, in particular a 10 alkyl, cycloalkyl or aryl group, or two groups R, attached to one and the same nitrogen atom, are interconnected to form a divalent hydrocarbon group containing from 2 to 8 carbon atoms and wherein x is a number from 2 to 8. One may mention in particular as examples of such vulcanization accelerators the compounds: dipentamethylene thiuram disulfide, dipentamethylene thiamuretetra sulfide , dipentamethylene thiamuramhexasulfide, tetrabutylthiuram disulphide, tetraethylthiuram disulfide and tetramethylthiuramide sulfide.

20

One can further cite as other examples of vulcanization accelerators which are sulfur donors and are useful for the formation of component A of the product M, alkylphenol disulfides and disulfides such as morpholine disulphide and caprolactam-N, Ν'-disulfide.

Preferred among the various mixtures capable of constituting the coupling agents of the invention are those which lead to rapid vulcanization and which limit the risk of pre-vulcanization.

8 DK 176109 B1

As previously stated, component B in the coupling agent consists of one or more vulcanizing agents selected from elemental sulfur and hydrocarbon polysulfides.

The sulfur used is advantageously sulfur plum, preferably sulfur crystallized orthorhombic and known by the name α-sulfur. In particular, component B of product M consists of sulfur that is orthorhombically crystallized.

The hydrocarbon polysulfides which can be used as vulcanizing agents in component B of product M or product D have the general formula:

R 1 - (S) m - <R 3 - (S) m) r - R2 wherein R 1 and R 2 each represent a monovalent saturated or unsaturated C 1 -C 20 hydrocarbon group or are interconnected to form a divalent saturated or unsaturated C 2 -C 20 hydrocarbon group , which forms a ring with the other 20 atoms combined in the formula, R 3 is a di valently saturated or unsaturated C 1 -C 20 hydrocarbon group, the groups - (S) m - denoting divalent groups each formed by m sulfur atoms, m may be different from one of these groups to the other, and denote a whole number of 25 numbers from 1 to 6, at least one m being equal to or greater than 2, and r denoting an integer which may have values from 0 to 10.

In the above formula, the monovalent C 1 -C 20 hydrocarbon groups R 1 and R 2 as well as the divalent C 1 -C 20 hydrocarbon groups R 3 are especially selected from aliphatic alicyclic acid groups. 9 DK 176109 B1 ke or aromatic groups. When the groups R 1 and R 2 are interconnected to form a divalent C 1 -C 20 hydrocarbon group forming a ring with the other atomic groups joined in the formula, this divalent group is similar to the group R, and it may also be of aliphatic , alicyclic or aromatic type. In particular, the groups R 1 and R 2 are identical and selected from C 1 -C 20 alkyl groups, e.g. ethyl, propyl, hexyl, octyl, nonyl, de-cyl, linear dodecyl ·,. tert-dodecyl, hexadecyl, octadecyl 10 and cycloalkyl groups and C6-C20 aryl groups, especially benzyl, phenyl, tolyl, cyclohexyl, while the group R3 or the divalent group formed by the compound of R 1 and R 2 selected from C 1 -C 20 alkylene groups or cycloalkylene group -per or arylene groups, especially C6-C20 phenylene groups, tolylene groups or cyclohexylene groups.

In particular, polysulfides useful in the invention are those defined by the formula: 20 R 1 - (S) n - R 2 wherein R 1 and R 2 each represent a monovalent saturated or unsaturated C 1 -C 20 hydrocarbon group or are interconnected to form of a C1-C20 divalent group R3, wherein Rx, R2 and R3 have the meaning previously defined, the term - (S) n ~ denotes a divalent group formed by a chain of n sulfur atoms, with n being an integer from 2 to 6th

Preferred polysulfides have the general formula: B1 R4 - (S) p - R4 wherein R4 represents a C1-C16 alkyl group and - (S) p- represents a divalent group formed by a chain formation of p 5 sulfur atoms, where p is an integer 2-5. Examples of such polysulfides are particularly dihexyldisulfid, dioctyldisul-FID, didodecyldisulfid, ditertdodecyldisulfid, dihexadi-cyldisulfid, dihexyltrisulfid, dioctyltrisulfid,-dinonyl trisulfide, ditertdodecyltrisulfid, dihexadicyltrisulfid, 10 dihexyltetrasulfid, dioctyltetrasulfid, dinonyltetrasul- fid, ditertdodecyltetrasulfid, dihexadecyltetrasulfid, dihexylpentasulfid, dioctylpentasulfid, dinonylpentasul -fid, ditertdodecylpentasulfide and dihexadecylpentasulfide.

Other polysulfides which may be used in accordance with the invention are e.g. such as diphenyltrisulfide, dibenzyltrisulfide, diphenyltetrasulfide, orthotolyl tetrasulfide, dibenzyltetrasulfide, dibenzylpentasulfide, dialylpentasulfide and tetramethyltetrathian.

20

The bitumen, which constitutes the majority of the bitumen polymer compositions of the invention, is selected from various bitumens having a penetration, as defined by the French standard NFT 66004, of between 5 and 25,500, preferably between 20 and 400. Such bitumen may in particular be bitumen produced by direct distillation or by reduced pressure distillation, or also blown or semi-blown bitumen having a penetration within the above ranges.

30 11 DK 176109 B1

The copolymer of styrene and of a conjugated diene used in the preparation of the bitumen polymer preparation is advantageously selected from sequence copolymers of styrene and butadiene, of styrene and of isoprene, of styrene and of chloroprene, of styrene and of carboxylated. butadiene or styrene and carboxylated isoprene. The copolymer of styrene and of conjugated diene, especially each of the copolymers mentioned above, has a weight content of styrene, preferably ranging from 15% to 40%. The viscosimetrically determined average molecular weight of the copolymer of styrene and of the conjugated diene, especially the molecular weight of the above copolymers, may advantageously be between 30,000 and 300,000 and preferably is between 70,000 and 200,000.

The copolymer of styrene and of conjugated diene is preferably selected from the di- or tri-sequence copolymers of styrene and of butadiene, of styrene and of isoprene, of styrene and of carboxylated butadiene, of styrene and of carboxylated isoprene containing styrene and molecular weights. which is within the ranges defined above.

The preferred amount of copolymers added to the bitumen is between 0.7 and 10% by weight of the bitumen.

In a preferred embodiment of the process of the invention, the copolymer and coupling agent are incorporated into the bitumen in the form of a stock solution of these two products in a solvent consisting of a hydrocarbon oil exhibiting an atmospheric pressure distillation range determined in accordance with U.S. Pat. 12 DK 176109 B1 standard ASTM D 86/67, which is between 100 ° C and 450 ° C, especially between 150 ° C and 370 ° C.

This hydrocarbon oil, which may be in particular a petroleum fraction of an aromatic nature, a petroleum fraction of 1 naphthenic-paraffinic nature, a petroleum fraction of a paraffinic nature, a petroleum fraction of a naphthenic-aromatic nature, a coal tar oil or also an oil of vegetable origin is sufficiently "heavy" to limit evaporation at the time of adding the stock solution to the bitumen, and at the same time it is sufficiently "light" to be removed to the greatest extent post-dispersion in the hot state of the bitumen polymer. composition containing it in such a way as to recover the same mechanical properties which would be present after the hot-state dispersion of a bitumen-polymer preparation prepared without making. use of the technique using a stock solution.

20

The stock solution is prepared by bringing the constituents constituting it, ie. the hydrocarbon oil serving as the solvent, the copolymer and the coupling agent contact with stirring at temperatures between 25 and 170 ° C, especially between 40 and 120 ° C, for a sufficient time, e.g. i from approx. 30 minutes to approx. 90 minutes to obtain a complete solution of the copolymer and of the coupling agent in the hydrocarbon oil.

The respective concentrations of the copolymer and of the coupling agent in the stock solution can vary widely as a function, in particular, of the nature of the hydrocarbon oil used to dissolve the copolymer and the coupling agent. Similarly, the respective amounts of the copolymer and of the coupling agent may advantageously be from 5% to 40% and 0.02 to 15% by weight of the hydrocarbon oil. A preferred stock solution comprises expressed as a weight percent of the hydrocarbon oil used as a solvent, 10-35% copolymer, and 0.1-5% coupling agent.

When the compositions of the invention are formed directly from the constituents bitumen, copolymer and coupling agent, it is preferable to work by first contacting the copolymer with bitumen in the selected proportions at a temperature between 100 ° C and 230 ° C and with stirring. sufficient time, generally in the range of a few minutes to a few hours, to form a homogeneous mixture, to which coupling agent is added to the obtained mixture, and to keep the total system 20 stirred at that temperature between 100 ° C and 230 °. C, e.g. corresponding to the temperature of the contacting between the copolymer and the bitumen, for a period of at least 10 minutes, generally from 10 to 90 minutes, to enable the coupling agent to release 25 radical sulfur and to initiate the radical sulfur thus produced on the on the one hand, the grafting of the copolymer on the bitumen and on the other the mutual bridging between the chains of this copolymer.

The quantities of copolymers contacted with the bitumen and of the coupling agent which is then added to the highly mature mixture of bitumen and that the copolymers in question are selected so as to be within the former of these quantities of defined intervals.

In order to prepare the bitumen polymer compositions of the invention, using the technique including stock solution, mix the stock solution of the copolymer and of the coupling agent with the bitumen, operating at a temperature between 100 ° C and 230 ° C. 10 while stirring, this being carried out e.g. by adding the stock solution to the bitumen which is kept under stirring at a temperature between 100 ° C and 230 ° C, maintaining the mixture obtained thereby with stirring at a temperature between 100 ° C and 230 ° C, e.g.

15 at the temperature used in mixing the stock solution to the bitumen for a period of at least 10 minutes and generally extending from 10 to 90 minutes, to enable the copolymer to graft through the coupling agent. 20 on the asphalt bitumen and the mutual bridging between the chains of the copolymer concerned.

The amount of stock solution mixed to the bitumen is selected so as to produce the desired amounts calculated relative to the bitumen of the copolymer and of the coupling agent, these amounts being within the ranges previously defined.

A particularly preferred embodiment of the preparation of bitumen polymer compositions according to the invention, including stock solutions, consists in that at a temperature between 100 ° C and 230 ° C and with stirring 80-95 wt. bitumen in contact with 20-5% by weight of stock solution, the latter serving as a solvent, expressed in% by weight of the hydrocarbon hydride 10-35% copolymer of styrene and of conjugated diene and 0.1-5 % coupling agent, keeping the mixture thus obtained under stirring at a temperature between 100 ° C and 230 ° C, and preferably at the temperature used for the contacting between bitumen 10 and the stock solution, for a period at least equal to And preferably between 10 and 60 minutes.

The bitumen-polymer compositions obtained by the method of the invention are useful for the preparation of various coatings, especially street and road coatings. The bitumen-polymer compositions of the invention prepared by the technique including stock solutions are particularly useful for this application, since they are directly applicable to classical dispersion methods.

The present invention is further illustrated by the following examples.

25

The rheological and mechanical characteristics of the bitumens or of the bitumen-polymer compositions to which reference will be made hereinafter are those defined above, namely penetration, softening point, Fraas point and rheological characteristics of tensile tests. .

EXAMPLE 1 16 DK 176109 B1

Preparation of a control bitumen polymer composition by directly incorporating the copolymer and of the coupling agent to the bitumen.

Mixing, operating at 170 ° C with stirring, 1000 parts by weight of a direct distillation bitumen with a penetration of. 82, a softening point at sphere-10 and the ring method at 48 ° C, a Fraas point equal to -18.5 ° C and a kinematic viscosity at 160 ° C of 1.7 x 10-4 m2 / s with 31 parts by weight of a two-sequence copolymer of styrene and of butadiene which exhibited a viscosimetric determined average molecular weight equal to ca. 75,000 and containing 25% by weight 15 styrene.

After 3 hours and 10 minutes mixing with stirring, a homogeneous mass was obtained.

To this mass maintained at 170 ° C, 1 part by weight of crystalline sulfur was then added and the total system was stirred for an additional 60 minutes to form the bitumen-polymer preparation.

Table I lists the essential characteristics of the bitumen-polymer preparation as obtained before and after being subjected to an aging test referred to as the "Rolling Film Oven Test" as defined in the US standard. ASTM D 2872. The bitumen polymer preparations before and after the aging test are designated respectively by the term "product lal" and "product Ia2". Table I also shows the corresponding characteristics of the starting material bitumen before and after aging experiments ("product Ibl" and "product Ib2", respectively).

It can be seen from the values shown in Table I that the use of a coupling agent consisting of crystalline sulfur leads to a bitumen-polymer composition whose elastomeric characteristics clearly distinguish it from bitumen (compare results obtained with tensile tests). .

Incidentally, the stability to aging of the bitumen polymer composition is improved over that observed for pure bitumen.

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EXAMPLE 2 19 DK 176109 B1

Preparation of a bitumen-polymer composition according to the invention by directly incorporating the copolymer and of the coupling agent into bitumen.

Proceed as described in Example 1, however, using as a coupling agent a mixture of 0.8 parts by weight of crystalline sulfur and 0.2. parts by weight of a sulfur donor vulcanization accelerator which consisted of tetramethylthiouram disulphide.

In Table II, for the bitumen polymer compositions obtained in Examples 1 and 2, characteristic properties analogous to those listed in Table I are listed.

The same notations symbolize the corresponding characteristics of the bitumen-polymer preparations before and after the aging test.

The use of a sulfur donor vulcanization accelerator mixed with crystalline sulfur to form the coupling agent leads, as can be seen from the values shown in Table II, to obtain a bitumen polymer composition exhibiting substantially improved elastomers. characteristics, especially at low temperature, relative to such values as are observed for the control bitumen-polymer preparation prepared using crystalline sulfur. Moreover, the stability against aging of the bitumen-polymer composition of the invention is clearly improved over the stability of the control-bitumen-polymer composition.

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EXAMPLES 3-4 21 DK 176109 B1

The preparation of bitumen polymer compositions according to the invention by directly incorporating the copolymer and the coupling agent into bitumen.

Proceed as described in Example 2, however, with certain variations which are defined hereafter, the other test conditions being the same as described in Example 2.

In Example 3, the coupling agent consisted of a mixture of 0.2 parts by weight of tetramethylthiuram disulfide and 0.7 parts by weight of crystalline sulfur and the temperature was equal to 160 ° C.

In Example 4, the coupling agent consisted of a mixture of 0.15 parts by weight of a sulfur donor vulcanization accelerator consisting of morpholine disulfide and 0.75 parts by weight of crystalline sulfur, the reaction being carried out at 140 ° C.

Table III shows the characteristics of the bitumen polymer compositions thus obtained before and after being subjected to aging experiments.

25

The bitumen polymer preparations before aging are designated "product P.a.l", while the corresponding bitumen polymer preparations after aging are designated "product P.a.2", P denoting the number of the example expressed in Roman numerals.

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EXAMPLE 5 23 DK 176109 B1

Preparation of a control bitumen polymer composition by the technique involving stock solution.

5 a - Preparation of stock solution

It was operated in a stainless steel reactor equipped with a stirrer and with a double wall which could be flowed through a heat transfer fluid.

The hydrocarbon oil used as the solvent to form the stock solution was a naphthenic / aromatic petroleum fraction which exhibited the following characteristics: - initial point of distillation after ASTM equal to 176 ° C.

20 - end point for distillation after ASTM equal to 352 eC

(measured in accordance with US standard ASTM D 86/67), flash point (French standard Luchaire NF T 60103) of 25 79 ° C, and - room weight (US standard ASTM D 1657-64) equal to 0.956.

24 DK 176109 B1

233 parts by weight of the petroleum fraction were introduced into the reactor and this petroleum fraction was heated while still stirring to a temperature of ca. 100 ° C by circulating a hot liquid in the double wall of the reactor.

5

Maintaining this temperature and stirring, 2 parts by weight of crystalline sulfur and 54 parts by weight of a powder made anti-caking with 2% by weight silica consisting of 10 a two-block copolymer of styrene were then introduced into the reactor. butadiene comprising 25 wt% styrene, and having a viscosimetric mean molecular weight of approx. 75 000.

After stirring for an hour at a temperature of approx. 100 eC 15 a homogeneous solution was obtained which was liquid at normal temperatures and characterized by the following values for the kinematic viscosity: - kinematic viscosity measured at 50 ° C: 12.10 x 10'4 20 m2 / s.

- kinematic viscosity measured at 100 ° C: 2.92 x 10'4 m2 / s.

This solution constituted the stock solution used for the preparation of the bitumen polymer preparation.

30 25 GB 176109 B1 b - Preparation of bitumen polymer preparation

One was pumped into a container equipped with a stirrer and equipped with steam reheaters at 170 ° C 1700 parts of a 5 direct distillation bitumen which exhibited the following physical properties from the beginning: - softening point (test with ball and ring): 48 ° C, 10 - Fraas - point: -18.5 ° C, - penetration: 82 1/10 mm, and - kinematic viscosity at 160 ° C: 1.70 x 10'4 m2 / s.

15

To the contents of the vessel maintained at 170 ° C with stirring were then added 300 parts by weight of the stock solution prepared as described above.

After 30 minutes of stirring at a temperature of 170 ° C, a liquid bitumen polymer preparation was obtained which exhibited a dynamic viscosity at 130 ° C equal to 0.098 Pa x s, i.e. a viscosity comparable to the viscosity exhibited by a bitumen having a penetration in the range of 180-220 and which could be added directly to a classic medium pressure dispenser.

Table IV lists the properties of the 30 bitumen polymer composition thus obtained before and after being subjected to a thermal treatment consisting of heating to 160 ° C in a furnace with a hermetic metallic container. containing the bitumen-polymer preparation and holding the container at this temperature for 60 days, this experiment making it possible to simulate the evolution of the product during prolonged storage. The bitumen polymer composition is denoted by the term "product V.a.l" before the thermal treatment and by "product V.a.2" after the thermal treatment.

10

Table IV also shows, for comparison purposes, before and after the above-mentioned thermal treatment, the corresponding characteristics of the bitumen used as the starting material which have been liquefied by 12% by weight, calculated in terms of the bitumen of the solvent used to form the stock solution ("Product Vb1" and "Product Vb2", respectively), as well as a bitumen-polymer preparation prepared in a similar manner to that described in Example 20 5; but omitting the crystalline sulfur ("product V.c.l" and "product V.c.2").

In the designation of the products, numbers 1 and 2 define the bitumen-polymer preparations before and after the thermal treatment, respectively.

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As can be seen by comparing the results contained in Table IV, the use of crystalline sulfur as a coupling agent in the technique using a stock solution leads to obtain a liquid bitumen polymer composition which exhibits elastomeric properties. After high temperature storage, this product provides a residual binder whose properties are in proximity to the properties of the bitumen polymer preparation prior to thermal treatment.

EXAMPLE 6

Preparation of a bitumen polymer composition according to the invention using the technique involving the use of stock solution.

Proceed as described in Example 5, however, forming the stock solution from 243.6 parts by weight of petroleum fraction, 54 parts by weight of two-sequence copolymers of styrene and of 20 butadiene, and a coupling agent consisting of 0.4 parts by weight of a sulfur donor vulcanization accelerator. and consisting of tetramethylthiuram disulphide and 1.5 parts by weight of crystalline sulfur.

Table V lists characteristics of the obtained bitumen polymer composition analogous to those shown in Table IV for the control preparation of Example 5, with Table V also including characteristics of the control preparation for ease of comparison.

30 29 DK 176109 B1

Examination of the results shown in Table V leads to the realization that the use of a coupling agent according to the invention in the technique of preparing bitumen polymer preparations using a 5 stock solution leads to the obtaining of a bitumen polymer. composition which exhibits clearly improved elastomeric characteristics, especially with respect to the breaking strength tr, relative to the breaking strength of the control bitumen-polymer preparation for the manufacture which (Example 5) uses only crystalline sulfur as coupling agent.

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Moreover, the stability of storage at a temperature of e.g. at 160 ° C for 2 months, of the bitumen-polymer composition of the invention (Example 6) greatly improved over the stability of the control preparation (Example 5), the elastomeric properties of the composition (VI.a.2) being as good as the values of the freshly prepared preparation (product Vl.al).

Claims (42)

A process for the preparation of bitumen polymer compositions, wherein, at a temperature between 100 ° C and 530 ° C, a mixture of bitumen with a block copolymer of styrene and of a conjugated diene, used in an amount of 0, is prepared. 5-15% by weight based on the bitumen content, and a coupling agent comprising a sulfur donor compound, thereby maintaining the mixture thus obtained in said tempera- ture selection and with stirring for at least 10 minutes, characterized in that the incoming coupling agent is selected from: the products M, which comprise 1-100% by weight of a component A consisting of one or more vulcanization accelerators which are sulfur donors and 99-0% of a component B consisting of one or more vulcanizing agents selected from elemental sulfur and hydrocarbon polysulfides; and using the coupling agent described in an amount appropriate to introduce such amount of sulfur as to make up 0.5 to 10% by weight of the copolymers used in the preparation of the bitumen polymer composition, provided that no alkaline compound is used. soluble in bitumen is added to the reactive medium when the coupling agent consists of a mixture of a sulfur donor vulcanization accelerator of the disulfide type and of elemental sulfur in a weight ratio accelerator to sulfur of between 40:60 and 80:20. Process according to Claim 1, characterized in that the incoming coupling agent is used in an amount suitable to provide an amount of sulfur constituting 1-8% by weight of that for the preparation of bitumen polymer. copolymer used. A method according to claim 1 or 2, characterized in that the incoming products M comprise 10 to 100% by weight of component A and 90 to 0% by weight of component B. Process according to any one of claims 1-3, characterized in that component A of product M consists of one or more vulcanization accelerators, which are sulfur donors, selected from the group formed by a) thiurampolysulfides of the formula: RSSR \ II II / N - C (S) - C - N / x \ 20. wherein the substituents R, which may be identical or different, each represent a hydrocarbon group, or are two substituents R bonded to the same nitrogen atom are interconnected to form a divalent C2-C8 hydrocarbon group, and x is a number from 2 to 8, b) alkylphenol disulfides and c) disulfides, and d) caprolactam-N, Ν'-disulfide. 30 DK 176109 B1! ! Process according to claim 4, characterized in that in the thiurampolysulfide formula, the hydrocarbon group R is a Cx / C8 group. 6. A process according to claim 4 or 5, characterized in that the group R is an alkyl, aryl or cycloalkyl group. Process according to any one of claims 1-6, 10, characterized in that component B, which is part of the composition of product M, consists of orthorhombic crystalline sulfur. Process according to any of claims 1-6, characterized in that the component B contained in the composition of the product M consists of or comprises one or more hydrocarbon polysulfides of the general formula: 20 Rx - (S). - (R3 - (S) Jr-R2 wherein R2 and R3 each represent a monovalent saturated or unsaturated C1-C20 hydrocarbon group, or are interconnected to form a divalent saturated or unsaturated C2-C20 hydrocarbon group forming a ring with the other atomic groups combined in the formula, R 3 is a divalent, saturated or unsaturated C 1 -C 2 hydrocarbon group, the groups - <S) m- represent divalent groups each formed by m sulfur atoms, m being different from a of 30 these groups to another, and m represents integers DK 176109 B1 from 1 to 6, at least one m being equal to or greater than 2, and r denoting an integer capable of assuming values from 0 to 10. Process according to claim 8, characterized in that the polysulfide (s) in question has the general formula: R4 - (S) p - R4 wherein R4 represents a C6-C16 alkyl group and - (S) p- represents a divalent group formed by a chain of p sulfur atoms, p being an integer 2 to 5. Process according to any one of claims 1-9, characterized in that the incoming bitumen has a penetration between 5 and 500. Process according to claim 10, characterized in that the incoming bitumen is selected from direct distillation or reduced pressure bitumens or blown or semi-blown bitumens. Process according to any one of claims 1-11, characterized in that the incoming copolymer is selected from the block copolymers of styrene and a conjugated diene selected from butadiene, isoprene, chloroprene, carboxylated budadiene and carboxylated isoprene. 30 DK 176109 B1 Process according to any one of claims 1-12, characterized in that the incoming copolymer has a weight content of styrene from 15% to 40%. Process according to any one of claims 1-13, characterized in that the incoming copolymer has a viscosimetric average molecular weight of between 30000 and 300000. that the average molecular weight is between 70000 and 200000. Process according to any one of claims 1 to 15, characterized in that the amount of copolymer added to bitumen is between 0.7 and 10% by weight based on the bitumen. Process according to any one of claims 1-16, 20, characterized in that the copolymer and the coupling agent are incorporated into the bitumen in the form of a stock solution of these two products in a solvent consisting of a hydrocarbon oil which exhibits a distillation interval at atmospheric pressure. which is between 100 25 ° C and 450 ° C. Process according to claim 17, characterized in that the distillation interval is between 150 ° C and 370 ° C. 30 DK 176109 B1 Process according to claim 17 or 18, characterized in that the hydrocarbon oil used is selected from aromatic petroleum fractions, naphthenic-paraffinic petroleum fractions, naphthenic-aromatic petroleum fractions, paraffinic petroleum fractions, coal tar oils and oils of vegetable origin. Process according to any of claims 17 to 10 19, characterized in that the tamper solution is prepared by contacting the components of the component with stirring at temperatures between 20 ° C and 170 ° C. Process according to claim 20, characterized in that the temperatures are between 40 ° C and 120 ° C. Process according to any one of claims 17-20, characterized in that the respective amounts of 20 copolymers and of coupling agent are 5-40% by weight and 0.2-15% by weight based on the hydrocarbon oil. Process according to claim 22, characterized in that the stock solution comprises 10-35% copolymer and 0.1-5% coupling agent calculated by weight of the hydrocarbon oil. Process according to any of claims 17-23, characterized in that at a temperature 30 between 100 ° C and 230 ° C and with stirring, 80-95 DK 176109 B1 wt% bitumen is contacted with 20-5 wt. -% stock solution, the latter comprising, expressed in terms of the weight of the hydrocarbon oil serving as solvent, 10-35% copolymer of styrene and of conjugated 5 diene and 0.1-5% coupling agent to hold the mixture thus obtained stirring at a temperature between 100 ° C and 230 ° C for a period of time at least equal to 10 minutes. Method according to claim 24, characterized in that the time course is between 10 and 60 minutes. Use of the bitumen-polymer compositions obtained by the method of any one of claims 1 to 15 in the production of coatings. Use according to claim 26, characterized in that the coatings produced are road surfaces. 28. Stock solution of polymers particularly useful in the preparation of bitumen polymer compositions comprising a hydrocarbon oil exhibiting a distillation inversion at atmospheric pressure of between 100 ° C and 450 ° C, and in solution in this oil a copolymer of the styrene and of a conjugated diene, and a coupling agent, the respective amounts of copolymer and coupling agent in solution being 5-40% by weight and 0.02-15% by weight based on the hydrocarbon oil, characterized in that the incoming coupling agent is selected from: the products M, 30 comprising by weight 1-100% by weight of a component A DK 176109 B1 consisting of one or more sulfur donor vulcanization accelerators and 99-0% by weight of a component B, which consists of one or more vulcanizing agents selected from elemental sulfur and hydrocarbon polysulfides. Stock solution according to claim 28, characterized in that the incoming products M comprise 10-100% by weight of component A and 90-0% by weight of component B. Stock solution according to claim 28 or 29, characterized in that component A is the compound defined in any of claims 4 to 6. Stock solution according to any one of claims 28 to 30, characterized in that component B of product M consists of orthorhombic crystalline sulfur. Stock solution according to any one of claims 28 to 20, characterized in that component B of the product M consists of or contains one or more of the polysulfides defined in claim 8. The stock solution of claim 32, characterized in that the polysulfide or sulfides are as defined in claim 9. Stock solution according to any of claims 28 to 33, characterized in that the copolymer is DK 176109 B1 selected from the block copolymers defined in claim 12. Stock solution according to any of claims 28 to 5, 34, characterized in that the copolymer contains 15 to 40% by weight of styrene. Stock solution according to any one of claims 28 to 35, characterized in that the copolymer has a viscosimetric mean molecular weight of between 30000 and 300000. The stock solution of claim 36, characterized in that the average viscosimetric molecular weight is between 70,000 and 200,000. 38. Stock solution according to any one of claims 28 to 37, characterized in that the hydrocarbon idol has a distillation range at atmospheric pressure of between 150 ° C and 370 ° C. The stock solution according to any one of claims 28 to 38, characterized in that the hydrocarbon oil is as defined in claim 19. Stock solution according to any one of claims 28 to 39, characterized in that it contains 10 to 35% copolymer and 0.1 to 5% coupling agent based on the weight of the hydrocarbon oil. A stock solution according to any one of claims 28 to 40, produced by contacting the ingredients which make up the solution with stirring at temperatures between 20 and 170 ° C. 5 42. Stock solution according to claim 41, characterized in that it is prepared at temperatures between 40 and 120 eC. -------