EP3008132A1

EP3008132A1 - Additives for industrial bitumen

Info

Publication number: EP3008132A1
Application number: EP14749871.1A
Authority: EP
Inventors: Gilles Barreto; Juan Antonio Gonzalez Leon
Original assignee: Carbonisation et Charbons Actifs CECA SA
Current assignee: Arkema France SA
Priority date: 2013-06-13
Filing date: 2014-06-10
Publication date: 2016-04-20
Also published as: WO2014199063A9; FR3007035A1; US20140366774A1; WO2014199063A1

Abstract

The present invention relates to industrial bitumen compositions, including at least one industrial bitumen and at least one surface-active agent for reducing the viscosity of said bitumen. The present invention also relates to the use of said industrial bitumen compositions for preparing products containing industrial bitumen as well as to the resulting products.

Description

ADDITIVES FOR INDUSTRIAL BITUMEN

The present invention relates to the field of industrial bitumens, in particular the use of specific surfactants for reducing the viscosity of these industrial bitumens, and more particularly bitumens useful for the production of impermeable or waterproof products. The present invention also relates to industrial bitumen compositions comprising at least one of said specific surfactants.

Impervious products include all types of products that are completely or at least partially liquid and / or gastight and / or temperature and / or noise-proof. As non-limiting examples, impervious products within the meaning of the present invention typically include roofing products, water repellents, noise damping products, thermal insulation products, adhesives, undercarriage putties for automotive industry, electrical cable joint protectors, joint fillers, bituminous marine mastics, for example those used for oil and gas pipeline joints, and the like.

These impermeable products generally contain at least one industrial bitumen and, in order to improve their rheological properties, different dispersed mineral and / or organic elements, such as particles, beads, flakes, aggregates, fibers. and the like.

Among the impervious products, roofing products are commonly and mainly divided into three main types, which are: multilayer roofing, bituminous membranes (mainly used for flat roofs or low slope) and shingles (mainly used for steep roofs). Membranes are mainly marketed in Europe, while shingles and multiple covers are mainly marketed in North America.

The membranes and shingles are generally prepared from a nonwoven support (fabric, polymer mat, organic or inorganic felt and the like) which is then saturated with one or more bituminous compositions, usually comprising at least one industrial bitumen. typically an oxidized bitumen. Additional layers of the same or other bitumen (s) or the same or other bituminous composition (s) can then be applied to the saturated support. These layers may include hard bitumen, oxidized bitumen, polymer modified bitumen and bitumen containing different mineral and / or organic dispersed elements. Reference articles relating to these roofing products and their manufacturing processes are for example, and without limitation, "Asphalt smoke exposures during the manufacture of asphalt roofing products" (Publication No. 2001 -127 by NIOSH (US), (2001), available at www.cdc.gov/niosh), and "The Bitumen Roofing Industry - A Global Perspective" published by the Asphalt Roofing Manufactures Association, 2nd edition, March 201 1, also available on the internet.

Bitumen or asphalt binders used for the aforementioned uses, sometimes called "roofing bitumens" for roofing products, include different types of bitumen. Bitumens which have undergone at least one chemical modification, such as oxidation, are most commonly used in order to improve their mechanical properties, such as ball-ring temperatures and also viscosity. The improvement of the mechanical properties of bitumens used for the preparation of impermeable products is necessary to avoid creep or any degradation (flow, breakage, melting, etc.) during use, caused by climatic conditions (rain, heat from sun and the like), fumes, oils, solvents and their vapors.

As a main drawback, during the preparation of said impermeable products, these bitumens having a high ball-ring temperature and / or viscosity must be heated to high temperatures, generally from about 180 ° C. to 200 ° C. or more, to achieve a bitumen viscosity level compatible with the manufacturing process and the desired production rate.

These high temperatures, which are necessary to effectively work these hard bitumens during the impregnation of the shingle or membrane support, involve a high energy consumption and generate fumes that can be dangerous for workers and the environment. . It should be noted that bituminous products, which are processed at temperatures above 200 ° C are outside the REACH registration compliance.

US6306937 clearly raises the problems of high viscosity bitumens used for roofing products and discloses known techniques for reducing the viscosity of hard bitumens, whether oxidized or not, said techniques using large amounts of solvents , such as white spirit solvents, and proposes to add polybutene to reduce the viscosity of bitumens at low temperatures. Other components may be added, such as known hydrophobic agents, as well as fatty acids and amines to facilitate the incorporation of polybutene into the bitumen. However, it is stipulated that the addition of polybutene as well as hydrophilic agents increases the viscosity at high temperatures and Large amounts of white spirit solvents are required to reduce the viscosity to acceptable levels in the examples.

CA1260653 discloses modified asphalt compositions for use as roofing materials, said compositions having low viscosity at elevated processing temperatures, while maintaining their mechanical properties at the temperatures of use. It is stipulated that the addition of 2% to 10% of a bis-stearoylamide is useful for reducing the viscosity of a bituminous composition for hiding application at processing temperatures. The practical reduction in viscosity shown in the examples is achieved by replacing a fully blown bitumen (high viscosity) with a mixture of fully blown and partially oxidized bitumen (lower viscosity) in the presence of the bis-stearoylamide additive. This additive is therefore not used to reduce the viscosity but to compensate for the reduction in the ball-ring temperature observed with the use of a partially oxidized bitumen.

Patent Application JP10182981A discloses a composition which can prevent an impervious layer of asphalt, useful as asphalt roofing material, from being deteriorated by alkaline water. This composition contains an acidic organophosphate having a P-OH radical comprising a long chain hydrocarbon intramolecular group in a ratio of 0.1% by weight to 5% by weight relative to the asphalted composition. The composition also contains an inorganic phosphorus compound, for example selected from phosphorus pentoxide (P2O5), polyphosphoric acid, phosphorus pentasulfide (P2S5), oxyphosphorus trichloride (POCI ₃ ) and phosphorus trichloride (PCI ₃ ), in a ratio of 0.075% by weight to 5% by weight relative to the asphalt composition. According to this disclosure, a fiber sheet saturated with a asphalted composition containing a mixture of an acidic organophosphate and an inorganic phosphorus compound, leads to a roofing material with an asphalted system, for which the degradation by the alkaline moisture can be prevented. However, it is currently known in the asphalt binder industry that inorganic phosphorus compounds in fact tend to increase the viscosity of an asphalt binder. These effects are for example described in FR-A-2065076 and in "Energy and Fuels", (2008), vol 22, page 2637 by JF Masson.

The additives which can reduce the viscosity of hard bitumens, while retaining the mechanical properties at application temperatures, can also be used to reduce the production temperature of bituminous products (thus improving the handling of products and the safety of the product. process). These additives can also be used to increase the production speed of products impervious, while continuing to work at conventional high temperatures, since viscosity is an important variable that directs the processing speed, for example the maximum rate at which impregnation of the bitumen into the support occurs.

There is therefore still, and this is a first objective of the present invention, a need for industrial bitumen compositions, such as hard bitumen compositions, and in particular oxidized bitumen compositions, which have a moderate to low viscosity at moderate to high temperatures.

As a second objective, the present invention aims to provide industrial bitumen compositions having a moderate to low viscosity at moderate to high temperatures and which can be easily prepared on an industrial scale.

A third objective is to provide industrial bitumen compositions, which allow rapid preparation of effective impervious materials, which can withstand all types of degradation (flow, rupture, fusion, etc.) during use, damage caused by climatic conditions (rain, heat of the sun, snow, cold, temperature variations and the like), fumes, oils, solvents and their vapors.

Yet another objective is to provide industrial bitumen compositions for the preparation of impermeable materials at reduced temperatures. Yet another object is to provide industrial bitumen compositions and impermeable materials containing said bitumen composition having less stress during their preparation and / or a lower heat shrinkage following the first cooling undergone during the process of manufacturing said impermeable materials. Yet another object is to provide industrial and waterproof materials containing said bitumen composition which are easier to recycle.

Yet another object is to provide industrial bitumen compositions which comprise one or more additives of low toxicity and preferably which are non-toxic or non-harmful to the environment, for humans and animals.

The inventors have now discovered that the above objectives are achieved in whole or in part by the oxidized bitumen compositions of the present invention, and which is explained and detailed below.

According to a first aspect, the present invention relates to a bituminous composition comprising:

(a) at least one industrial bitumen, and

b) at least one surfactant. Industrial bitumens are all types of bitumen that are not intended to prepare asphalt for the construction of roads. More specifically, industrial bitumens are hard bitumens at the application temperature, such as, for example, fully or partially oxidized oxidized bitumens and more generally bitumens of high bead ring temperature, that is to say bitumens which have generally a ball-ring temperature substantially higher than the bitumens useful for road construction. "Hard bitumens" are well known to those skilled in the art and readily available from bitumen plants as described in standard NF EN 13305 (September 2009).

According to a preferred embodiment, "industrial bitumen" means a bitumen having a bead-ring temperature ranging from 50 ° C. to 180 ° C., preferably from 50 ° C. to 170 ° C., more preferably 70 ° C. at 160 ° C, still more preferably from 80 ° C to 150 ° C inclusive. "Ball-ring temperature" is the temperature at which a disk of the test material is soft enough to allow a steel ball to fall, wrapped in the bituminous binder, a distance of 25 ± 0.4 mm. For this invention, the ball-ring temperature is measured according to standard NF EN 1427 of June 2007 using an automatic ball-ring apparatus (for example an instrument Normalab Analis NBA440 instrument) with glycerol as a bath liquid.

In the present invention, "oxidized bitumen" represents any hard bitumen obtained by any chemical and / or physical treatment in such a way that, with respect to an untreated bitumen, it contains an increased proportion of asphaltenes, an decreased proportion of naphthenes and polar aromatics and the same proportion of saturated substances, as described in "The Bitumen Roofing Industry - A Global Perspective", published by the Asphalt Roofing Manufactures Association, 2nd Edition, March 201 1.

The oxidation of the bitumen can be carried out by several artificial means, such as the direct reaction with air, with or without catalysts at high temperatures, preferably from 200 ° C to 280 ° C inclusive. The oxidation process can, however, occur "naturally" by exposing the bitumen or asphalt binder to air at room temperature for a very long time. The bituminous binders present in road coatings after several years of use are therefore also considered oxidized bitumens in the context of the present invention.

[0024] Preferably, "oxidized bitumen" for use in the compositions of the present invention comprise bitumens or asphalts completely or partially blown in air which may or may not contain other additives such as polymeric modifiers, also known as bitumen modification polymers, as explained hereinafter.

The bitumens that can be used to prepare the "oxidized bitumens" defined above are any types of bitumen or asphalt binders, and preferably bitumens selected from products obtained from petroleum by direct distillation. or by distillation of petroleum at reduced pressures, products obtained by extraction of tars and oil sands, oxidation and / or fluxing products with carbonaceous solvents, including paraffins and waxes of these bituminous materials, bitumens synthetic materials (as described in document FR 2 853 647 A1), tars, oily resins or indene-coumarone resins mixed with aromatic and / or paraffinic hydrocarbons, mixtures thereof and mixtures thereof. bituminous materials with acids and the like. These bitumens are modified in "oxidized bitumens" defined above by any techniques known to those skilled in the art, for example those described in "The Bitumen Roofing Industry - A Global Perspective", ibidem.

The composition of the present invention therefore comprises at least one industrial bitumen, preferably at least one hard bitumen and in particular at least one oxidized bitumen as defined above and at least one surfactant. The surfactants that can be used are all types of known surfactants. Preferred surfactants are organic compounds comprising at least one hydrophilic moiety and at least one lipophilic moiety.

In the context of the present invention, "hydrophilic moiety" means any fragment of the surfactant that is not a lipophilic moiety. "Lipophilic moiety" means any portion of the surfactant consisting solely of carbon atoms and hydrogen atoms and wherein 3 or more carbon atoms are directly bonded to one another via a single, a double and / or a triple bond, and the hydrocarbon chain of 3 or more carbon atoms may be a combination or not of linear, branched and / or cyclic chains.

According to a preferred embodiment, the surfactants for use in the present invention are those having at least one, preferably at least two, more preferably more than two and even more preferably all the following characteristics:

1) the surfactant comprises at least one lipophilic moiety for each individual hydrophilic moiety; 2) the surfactant comprises at least one lipophilic moiety which is an aliphatic or unsaturated or aromatic hydrocarbon chain comprising 6 or more carbon atoms;

3) the surfactant is an organic compound comprising at least one heteroatom, preferably at least two heteroatoms, selected from oxygen, nitrogen, phosphorus and sulfur;

4) the surfactant is an organic compound having a molecular weight ranging from 50 daltons to 2000 daltons, preferably from 150 daltons to 1500 daltons and more preferably from 250 daltons to 1000 daltons inclusive;

5) the surfactant comprises at least one oxygen atom and the ratio of the total number of oxygen atoms (O) to the total number of carbon atoms (C) is such that 0 <O / C <0 , 5, preferably 0 <0 / C <0.33;

6) the surfactant comprises at least one oxygen atom and at least one nitrogen atom, and the ratio of the total number of oxygen atoms (O) to the total number of nitrogen atoms (N) is such that 1 <N / O <4, preferably 1 <N / O <3.

Preferred surfactants for use in the present invention are those having the characteristics 1), 2) and 3) as defined above. Surfactants most preferred for use in the present invention are those having the characteristics 1), 2), 3) and 4) as defined above.

According to another preferred embodiment, the surfactants for use in the present invention are organic compounds comprising at least one chemical group selected from C = 0, S = 0 and P = 0.

According to another preferred embodiment, the surfactants for use in the present invention comprise only a lipophilic moiety containing at least 4 carbon atoms when there is more than one amide fragment, "amide fragment" meaning a -C (= O) -N group in a linear (i.e. non-cyclic) chain.

According to another preferred embodiment, the surfactant is an organic compound comprising at least two heteroatoms chosen from oxygen, nitrogen, phosphorus and sulfur and having any of the other characteristics listed. above.

According to another preferred embodiment, the surfactants for use in the present invention do not contain any -NH ₂ group.

According to yet another preferred embodiment, the surfactant intended for use in the composition of the present invention is a fatty acid chosen from, by way of nonlimiting examples, saturated linear or branched carboxylic acids. or partially unsaturated, C ₆ -C ₃ O, preferably C ₈ -C ₂₆ . Examples of these fatty acids include caproic, caprylic, pelargonic, capric, undecylic, lauric, tridecylic, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, arachidic, arachidonic, cerotic, montanic and melissic acids and their derivatives. mixtures.

According to yet another embodiment, the surfactant intended for use in the composition of the present invention is a fatty amide chosen from linear or branched, saturated or partially unsaturated, unsubstituted, monosubstituted or disubstituted alkylamides. C ₆ -C ₃ o, preferably C ₈ -C ₂₆ . Examples of these fatty amides include, in an illustrative and nonlimiting manner, hexanamide, heptanamide, octanamide, nonamide, decenamide, undecenamide, dodecenamide, 9c-dodecenamide, tridecenamide, tetradenenamide 9c-tetradecenamide, hexadecenamide, 9c-hexadecenamide, octadecenamide, 6c-octadecenamide, 9c-octadecenamide, 12-hydroxy-9c-octadecenamide, 9c, 12c, 15c-octadecenamide, nonadecenamide, eicosanamide, and mixtures thereof.

As another preferred embodiment, the surfactant is chosen from the esters of phosphoric acid and preferably from the (di) alkyl phosphate esters, still more preferably the alkoxylated esters of (di) alkylphosphate, such as ethoxylated, propoxylated and / or butoxylated esters of (di) alkylphosphate, such as, for example, those described in WO 2008/148974. Examples of alkoxylated alkyl phosphate esters are ethoxylated alkyl phosphate esters and mixtures thereof, a typical example being the CECABASE ^® RT BI09 available from CECA SA.

According to another preferred embodiment, the surfactant intended for use in the present invention comprises at least one, and preferably one, five or six membered heterocyclic ring containing nitrogen and optionally, but preferably, an amide group. Examples of such surfactants include linear or branched C ₆ -C ₃ , preferably C ₈ -C ₂ 6 alkylamidoalkyleneimidazolidinones, for example N- [2- (2-oxo-1-imidazolidinyl) ethyl] -9-octadecenamide (CAS 87041 - 09-6), linear or branched alkylènepipérazines alkylamido-C ₆ -C ₃ o, preferably C ₈ -C ₂ 6, e.g. CECABASE ^® 280, available from CECA SA, and their mixtures.

Another embodiment of the present invention uses surfactants chosen from carboxylic acid salts of amines and diamines, such as di (fatty carboxylate) alkyldiamine salts. Examples of these dicarboxylic acid diamine salts include Inipol ^® and 002 ^® Inipol OT2 available from CECA SA, and mixtures thereof. [0039] Yet another embodiment of the present invention uses surfactants chosen from alkoxylated amines and alkoxylated polyamines, such as ethoxylated and / or propoxylated and / or butoxylated fatty alkylamines and ethoxylated and / or propoxylated fatty alkylpolyamines. and / or butoxylated, eg Dinoramox ^® S12, the Dinoramox ^® S7 available from CECA SA, and the like, and mixtures thereof.

According to another preferred embodiment, the surfactants intended for use in the present invention do not lose more than 15% of their weight, preferably not more than 10%, more preferably not more than 5% of their weight. weight at 200 ° C when subjected to standard thermogravimetric analysis in air (1 L / h) at a heating rate of 2 ° C / min.

According to another preferred embodiment, the surfactants intended to be used in the present invention decrease by 20%, preferably by 40%, more preferably by 50%, most preferably by 60% the viscosity of a industrial bitumen as measured in a dynamic shear rheometer at 150 ° C at a shear stress of 0.1 sec ^-1 using a parallel plate geometry (diameter 25 mm) after being heated for 20 minutes at the same temperature.

The amount of surfactant (s) present in the composition of the present invention may vary in large proportions. However, the amount of surfactant (s) is indeed lower than would be the necessary amount of a conventional solvent to reduce the viscosity of said bitumen. Consequently, the amount of surfactant (s) present in the composition of the invention generally ranges from 0.1% by weight to 4% by weight, limits included, relative to the weight total of said composition, preferably from 0.3% by weight to 3% by weight, inclusive, and even more preferably from 0.5% by weight to 2% by weight, inclusive, relative to the total weight of said composition; composition. A smaller amount of surfactant (s) would not lead to an effective reduction in the viscosity of industrial bitumen and a higher amount could act as a liquid solvent and affect the mechanical properties of the bitumen at application temperatures.

The composition of the present invention may further comprise other additives known to those skilled in the art, such as, for example, and preferably chosen from polymers, fibers, clays, minerals, fillers, carbon nanotubes, glass fibers, wood pulp, ground rubber, organic tackifiers and the like as well as mixtures thereof. However, inorganic additives containing phosphorus and in particular those chosen from phosphorus pentoxide (P2O5), polyphosphoric acid, phosphorus pentasulfide (P2S5), Oxyphosphorus trichloride (POCI ₃ ) and phosphorus trichloride (PCI ₃ ) are not preferred as other additives. When such inorganic additives containing phosphorus are present in the composition of the invention, their proportion should not exceed 0.07% by weight relative to said industrial bitumen composition.

Therefore, and as a preferred embodiment, the present invention relates to a bituminous composition comprising at least one industrial bitumen as defined above, at least one surfactant as defined above and optionally at least one additive. inorganic phosphorus, selected from phosphorus pentoxide (P2O ₅ ), polyphosphoric acid, phosphoric acid, phosphorus pentasulfide (P ₂ S ₅ ), oxyphosphorus trichloride (POCI ₃ ) and phosphorus trichloride (PCI ₃ ) in an amount of less than 0.07% by weight relative to the total weight of the bituminous composition.

The polymers that may be present in the compositions of the present invention are any types of polymers, preferably polymeric modifiers, also known as bitumen modification polymers.

These polymers, linear or branched and / or chemically crosslinked, are well known to those skilled in the art and include, as non-limiting examples, polybutadiene, polyisoprene, polychloroprene and their hydrogenated versions, polyisobutylene , block copolymers of polybutadiene and isoprene with styrene, and their hydrogenated versions, such as poly (styrene-b-butadiene) (SB), poly (styrene-b-butadiene-b-styrene) ( SBS), poly (styrene-b-isoprene-b-styrene ((SIS), poly (styrene-b- (isoprene-stat-butadiene) -b-styrene) or poly (styrene-b-isoprene-b - butadiene-b-styrene) (SIBS), hydrogenated SBS (SEBS), poly (styrene-b-butadiene-b-methyl methacrylate ((SBM), its hydrogenated version (SEBM), poly (methyl methacrylate) -b-butyl acrylate-b-methyl methacrylate) (MAM), poly (styrene-b-butyl acrylate-b-styrene ((SAS), random copolymers of butadiene with styrene (SBR) and acrylonitrile (NBR) and their hydrogenated versions, butyl rubber or a halogenated rubber, polyethylene, polypropylene, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer and ethylene-propylene-diene copolymer (EPDM), copolymers of ethylene with acrylic monomers, copolymers of ethylene and acrylic esters, copolymers of ethylene, acrylic ester, maleic anhydride, copolymers of ethylene, acrylic ester, functionalized acrylic esters, such as acrylate or glycidyl methacrylate, available from the company Arkema under the trade name LOTADER®, polymers or acrylic or methacrylic copolymers such as resins based on (meth) acrylic esters, such as poly (butyl acrylate) and its copolymers with styrene, methyl methacrylate or other acrylic monomers, and mixtures thereof.

The composition of the present invention may be prepared by any method known to those skilled in the art. Advantageously, the surfactant (s) is (are) added to an industrial bitumen which has been previously heated to a temperature ranging from 150 ° C to 250 ° C. Other additives, such as those described above, may be added preferably at the same time or before or after the surfactant (s). The addition of the surfactant (s) and any other additives is carried out with stirring, or simultaneous or sequential addition of said additives, according to one or more known conventional techniques and for example using a mechanical stirrer and / or recirculation by a pump.

In another aspect, the present invention relates to the use of at least one surfactant as defined above for lowering the viscosity of a bituminous composition comprising at least one industrial bitumen, preferably a hard bitumen, more preferably an oxidized bitumen.

As described above, the hard or oxidized industrial bitumens are highly viscous at high temperatures, that is to say that the oxidized bitumens are of a much higher viscosity than the unoxidized bitumen corresponding to the same. temperature. The inventors have surprisingly discovered that the addition of at least one surfactant in an industrial bitumen, preferably hard, more preferably oxidized, allows a significant decrease in the viscosity of said oxidized bitumen.

The addition of at least one surfactant as defined above, in an amount of 0.1% by weight to 4% by weight, inclusive, preferably 0.3% by weight to 3% by weight, limits included, and more preferably from 0.5% by weight to 2% by weight, limits included, in a bituminous composition comprising at least one industrial bitumen as defined above leads to a decrease in the viscosity of said bituminous composition as described above.

For the purpose of the present invention, the reduction of the viscosity (RV) is the ratio defined by the following formula:

there

RV = - ^ - where V _S A is the value of the viscosity of the bituminous composition containing the industrial bitumen a) and the surfactant b) and

VIB is the viscosity value of said industrial bitumen a), and where V _S A and VIB are measured in a dynamic shear rheometer at 150 ° C and a shear stress of 0.1 sec- ¹ , using a parallel plate geometry (25 mm diameter) after submitting to a heating for 20 minutes at the same temperature.

The present invention therefore also relates to bituminous compositions comprising at least one industrial bitumen as defined above and at least one surfactant which allows a reduction in viscosity (RV as defined above), such that:

0 <RV <0.8, preferably 0 <RV <0.6, more preferably 0 <RV <0.5, most preferably 0 <RV <0.4.

In contrast to the teaching of the prior art (see for example WO 2008/148974), where surfactants, such as phosphate esters, do not modify the viscosity of conventional bitumens, it is It has now been shown that surfactants have an effect on the viscosity of oxidized bitumens: as stated above, the viscosity is lowered substantially.

Decreasing the viscosity of industrial bitumens without modifying or substantially modifying their other mechanical properties has long been a problem in the industry and the present invention now solves this problem in a simple and effective manner. The preparation of products containing industrial bitumen, such as impervious materials, and the like, with the compositions of the present invention can now be carried out at lower temperatures, thereby avoiding toxic and dangerous fumes and saving heating energy.

Alternatively, the preparation of industrial bitumen-containing products and the like with the compositions of the present invention can now be carried out at elevated temperatures, even allowing a lower viscosity, compared to said non-agent containing bitumens. surfactants and therefore faster preparation processes and therefore more economical.

With the bituminous compositions of the invention, it is also possible to combine the two advantages above for the production of products containing industrial bitumen, in particular impervious products, that is to say, to combine the lowering the production temperature and at the same time increasing the speed of production.

Alternatively, the preparation of products containing industrial bitumen, such as impermeable materials, and the like with the compositions of the present invention can now be carried out at elevated temperatures, thus allowing even a lower viscosity, relative to said industrial bitumens not containing surfactants. As an advantageous consequence, lower stresses and / or lower heat shrinkage are observed during the production process of industrial bitumen-containing products, during cooling and, typically during the production process of impervious products such as shingles or membranes. The bituminous composition described in the present invention can thus be applied to a substrate to produce an impermeable product, wherein the substrate or support may have been previously treated with another coating. Non-limiting examples of supports include floors, walls, roofs, ceilings, tubes, and organic or inorganic supports, flexible, woven or non-woven, such as cellulose fibers, glass fibers, as well as felts, for example polyester felts. It has been observed, as another advantage, that the surfactant present in the bituminous composition of the invention allows a better wettability of said substrate or support.

The bituminous compositions of the invention can therefore also provide additional advantages during production and for the final properties of products containing industrial bitumen, since lesser stresses must be applied, for example on a nonwoven support for production of shingles, membranes and the like. Similarly, production at lower temperatures when using the bituminous compositions of the invention results in lower residual heat stresses on products containing industrial bitumen, thus improving their final mechanical properties.

As another advantage of the present invention, products containing industrial bitumen, such as impermeable materials, prepared from at least one composition according to the present invention, are easy to recycle or are recycled in a more simple manner by compared to products containing industrial bitumen which do not include the composition of the present invention, due to the lower viscosities at the temperatures of the recycling processes.

Therefore, and in another aspect, the present invention relates to the use of at least one industrial bitumen composition as described above for the preparation of products containing industrial bitumen, such as impermeable materials, including, but not limited to, roofing, waterproofing and other water repellents, asphalt shingles, polymer-modified bitumen roofing products, roll roofing products, membranes , adhesives, pipe coatings, hydraulic products, paving mixes, channel, ditch and pond coverings, dam and bridge protections, hydrophobic paints, electrical cable joint protections, oil and gas pipeline joints, joint filling compounds, sound insulation products, reinforcement and underlay felts, lower protections for concrete based coatings Portland cement and the like.

According to yet another aspect, the present invention relates to a product containing industrial bitumen, such as an impermeable material, as listed above.

The present invention is further illustrated by the following examples which are not intended to limit the intended range of protection which is defined in the appended claims.

Example 1

Bituminous compositions are prepared as follows: 100 g of a 100/40 oxidized bitumen having a ring-ball temperature of 114 ° C. (bitumen A) in a metal container is heated at 180 ° C. in a furnace while 2 hours. Then, the container is taken from the oven and placed on a mechanical stirring apparatus equipped with a temperature controlled heating plate. When the temperature is stabilized at 180 ° C, the additive is introduced with stirring. The mixture is then stirred for a further 10 minutes, the stirring is stopped and the samples are poured onto a silicone mold. The samples are stored for 24 hours at 18 ° C overnight before measuring their viscosity using an Anton Paar MCR301 dynamic shear rheometer. The viscosity of the compositions is measured at 150 ° C. as a function of a shear stress of 10 sec ^-1 to 0.1 sec -1 using a parallel plate geometry (diameter 25 mm) after having been subjected to heating for 20 min at the same temperature.

The compositions tested are:

• Bitumen A pure, that is to say without additive;

• Bitumen A + 3% by weight of Solvent 1, which is the rapeseed oil methyl ester (commercially available under the name Solvester);

Bitumen A + 1% by weight of surfactant 1, which is N- [2- (2-oxo-1-imidazolidinyl) ethyl] -9-octadecenamide (CAS 87041-096-6); and

• Bitumen A + 3% by weight of surfactant 1.

The attached FIG. 1 shows the viscosity at 150 ° C. as a function of shear stress of each bituminous composition comprising bitumen A with the indicated amounts of solvent 1 and surfactant 1.

It is clear from this FIG. 1 that there is an influence of the shear stress on the viscosity of pure bitumen A, having a greater value at a higher temperature. low shear stress. The composition containing 3% by weight of solvent exhibits a behavior similar to that of pure bitumen A at a viscosity slightly lower than the lower shear stresses. The compositions containing surfactant 1 according to the present invention show a significant decrease in the viscosity of bitumen A.

With 1% by weight of Surfactant 1, the decrease in viscosity is significantly greater than that obtained with 3% by weight of Solvent 1. The composition having 3% by weight of surfactant 1 (same amount that for the composition with Solvent 1), displays an even greater decrease in viscosity, which is more than an order of magnitude lower than pure bitumen at lower shear stresses. It is also interesting to point out the shape of the curve which is different for the composition containing 3% by weight of surfactant 1, corresponding to a lower sensitivity to the shear stress.

This example clearly shows that the present invention is not based on dissolution or fluxing, as in the case of a simple solvent, but that there is indeed a surprising effect related to the addition of a surfactant that actually appears to interact with the oxidized bitumen, resulting in a valuable decrease in its viscosity.

Example 2

Bituminous compositions comprising a blown bitumen R100-40 supplied by Shell (Bitumen B) are prepared by adding respectively 1% by weight and 2% by weight of surfactant 2 available under the name Cecabase ^® RT BI09 at CECA. SA One and two grams of Surfactant 2 were added respectively to 100 g of bitumen B, heated to 180 ° C and stirred using a mechanical stirrer in a manner similar to that described in Example 1.

[0070] The appended FIG. 2 shows the viscosity of the composition comprising bitumen B with the indicated amounts of Surfactant 2, at a shear stress of 10 [1 / s] as a function of the temperature of the bituminous composition, measured using an Anton Paar MCR301 dynamic shear rheometer using parallel plate geometry (diameter 25 mm).

It can be observed that the viscosity of pure bitumen B is relatively sensitive to the temperature multiplying its value relatively significantly by a factor of 3 at a difference of only 20 ° C. Conversely, the compositions according to the present invention, that is to say containing a surfactant, respectively at 1% by weight and 2% by weight not only show a significantly higher viscosity. low at all temperatures tested but also a significantly less significant influence of the temperature on the viscosity. This illustrative example of the invention clearly shows that a process for preparing a product containing oxidized bitumen can be carried out at reduced temperatures of about 20 ° C or higher since the viscosity is well below these low temperatures. to that of pure oxidized bitumen. It is also possible to carry out such a method of preparation at higher temperatures, where the viscosity of the compositions of the present invention is always lower than that of pure oxidized bitumen, the advantage of these lower viscosities being a flow, a mixture, a coating and the like easier and faster.

Example 3

[0072] Nine bituminous compositions (Composition 1 to Composition 9) comprising a blown bitumen R100-40 supplied by Shell (Bitumen B) are prepared in a manner similar to Example 2, in order to evaluate the effect of the addition of a surfactant on the viscosity of an industrial bitumen. The samples of these compositions are stored for 24 hours at 18 ° C. before measuring their viscosity using an Anton Paar MCR301 dynamic shear rheometer. The viscosity of the pure bitumen and each of the compositions is measured at 150 ° C. at a shear stress of 0.1 sec ^-1 using a parallel plate geometry (diameter 25 mm) after having been heated for 20 minutes. at the same temperature.

The compositions 1 to 6 are the following:

Composition 1 (according to the invention): 1% by weight of Surfactant 1, as in Example 1;

Composition 2 (according to the invention): 1% by weight of surfactant 2, which is Cecabase® RT BI09, available from CECA S.A .;

Composition 3 (according to the invention): 1% by weight of Surfactant 3, which is Surfaline® TS18L from CECA S.A. (ethoxylated tristyrylphenol);

• Composition 4 (according to the invention): 1% by weight of Surfactant 4, which is Dinoramox® S12 from CECA S.A. (ethoxylated alkylamine);

Composition 5 (according to the invention): 2% by weight of Surfactant 5, which is Inipol® 002 from CECA S.A. (diamine dioleate);

Composition 6 (according to the invention): 2% by weight of surfactant 6, which is an octadecanamide (technical grade) of Sigma-Aldrich.

Composition 7 (comparative example): 1% by weight of surfactant 7, which is a surfactant based on a poly (ethylene oxide) / poly (propylene oxide) block copolymer prepared by ethoxylation (18). units of ethylene oxide) of a monobutyletherpolypropyleneglycol with a total molar mass of 3218 g / mol and an O / C ratio of 0.364;

• Composition 8 (Comparative Example): 1% by weight of surfactant 5, which is the oleic acid amide of tetraethylenepentamine (CAS No. 68953-36-6). This surfactant has a N / O ratio of 5.

• Composition 9 (comparative example): 1% by weight of surfactant 2, and 0.4% by weight of phosphorus pentoxide.

Table 1 below shows the RV viscosity ratio measured for each of compositions 1 to 9.

- Table 1:

These results show that the compositions 1 to 6 according to the invention effectively lower the viscosity of an oxidized bitumen, highlighting the fact that from 1% by weight of the surfactant according to the invention, the viscosity of an industrial bitumen is surprisingly and very strongly lowered.

These results also show that the surfactants which are outside the scope of the present invention are either less effective or result in an increase in the viscosity at the same concentrations. In particular, the composition 9 has a high viscosity, more than 6 times higher than the viscosity of pure bitumen. This result demonstrates the dramatic effect on viscosity when inorganic phosphorus compounds are present in industrial bitumen compositions.

Claims

A bituminous composition comprising:

(a) at least one industrial bitumen, and

b) at least one surfactant.

Bituminous composition according to claim 1, said at least one surfactant having at least one, preferably at least two, more preferably more than two and even more preferably all of the following characteristics:

1) the surfactant comprises at least one lipophilic moiety for each individual hydrophilic moiety;

2) the surfactant comprises at least one lipophilic moiety which is an aliphatic or unsaturated or aromatic hydrocarbon chain comprising 6 or more carbon atoms;

3. Bituminous composition according to claim 1 or 2, the amount of surfactant (s) ranging from 0.1% by weight to 4% by weight, preferably from 0.3% by weight to 3% by weight. % by weight and more preferably from 0.5% by weight to 2% by weight relative to the total weight of the bituminous composition.

Bituminous composition according to any one of the preceding claims, further comprising other additives, preferably chosen from polymers, fibers, clays, minerals, fillers, carbon nanotubes, glass fibers, mechanical pulp, milled rubber, organic tackifiers and the like as well as mixtures thereof.

5. Bituminous composition according to any one of the preceding claims, optionally further comprising at least one inorganic phosphorus additive, selected from phosphorus pentoxide (P2O ₅ ), polyphosphoric acid, phosphoric acid, phosphorus pentasulfide. (P2S ₅ ), oxyphosphorus trichloride (POCI ₃ ) and phosphorus trichloride (PCI ₃ ) in an amount of less than 0.07% by weight relative to the total weight of the bituminous composition.

6. Bituminous composition according to any one of the preceding claims, said at least one industrial bitumen being a hard bitumen.

7. Bituminous composition according to any one of the preceding claims, said at least one industrial bitumen being an oxidized bitumen.

Bituminous composition according to any one of the preceding claims, said at least one industrial bitumen having a ball-and-ring temperature ranging from 50 ° C to 180 ° C, preferably from 50 ° C to 170 ° C, more preferably from 50 ° C to 150 ° C, terminals included.

9. Bituminous composition according to any one of the preceding claims, said at least one surfactant being a fatty acid selected from linear or branched, saturated or partially unsaturated C ₆ -C ₃ o, preferably C ₈ - _C2 6, preferably selected from caproic, caprylic, pelargonic, capric, undecylic, lauric, tridecylic, myristic, myristoleic, palmitic, palmitoleic, stearic, oleic, ricinoleic, linoleic, arachidic, arachidonic, cerotic, montanic and melissic, and their mixtures.

10. bituminous composition according to any one of claims 1 to 8, said at least one surfactant being a fatty amide selected from alkylamides linear or branched, saturated or partially unsaturated, unsubstituted, monosubstituted or disubstituted C ₆ -C ₃ o, preferably C ₈ -C ₂ 6, and preferably selected from hexanamide, the heptanamide, the octanamide the nonamide the decenamide, the undécénamide the dodécénamide, 9c-dodécénamide the tridécénamide, tetradecenamide, 9c- tetradecenamide, hexadecenamide, 9c-hexadecenamide, octadecenamide, 6c-octadecenamide, 9c-octadecenamide, 12-hydroxy-9c-octadecenamide, 9c, 12c, 15c-octadecenamide, nonadecenamide, eicosanamide, and their mixtures.

11. Bituminous composition according to any one of claims 1 to 8, said at least one surfactant being selected from phosphoric acid esters and preferably from (di) alkyl phosphate esters, still more preferably from alkoxylated esters (di) alkylphosphate.

The bituminous composition according to any one of claims 1 to 8, said at least one surfactant comprising at least one, and preferably a five or six membered, nitrogen-containing heterocyclic ring and optionally, but preferably an amide group, said at least one surfactant being preferably chosen from linear or branched C ₆ -C ₃ o, preferably C ₈ -C ₂ 6 alkylamido-alkyleneimidazolidinones, linear or branched alkylamidoalkylenepiperazines. C ₆ -C ₃ o, preferably C ₈ -C ₂ 6 and mixtures thereof.

13. bituminous composition according to any one of claims 1 to 8, said at least one surfactant being selected from carboxylic acid salts of amines and diamines, such as di (fatty carboxylate) alkyldiamine salts; .

14. Bituminous composition according to any one of claims 1 to 8, said at least one surfactant being chosen from ethoxylated and / or propoxylated and / or butoxylated fatty alkylamines and ethoxylated and / or propoxylated and / or butoxylated fatty alkylpolyamines.

15. Use of at least one surfactant for lowering the viscosity of a bituminous composition comprising at least one industrial bitumen, preferably a hard bitumen, more preferably an oxidized bitumen, said at least one surfactant being as defined in US Pat. Claims 2 to 14.

16. Use of the bituminous composition according to any one of claims 1 to 14, for the preparation of a product containing industrial bitumen.

17. Use according to claim 16, the product containing industrial bitumen being an impermeable product and preferably an impervious product chosen from the products roofing, waterproofing and other waterproofing products, asphalt shingles, polymer-modified bitumen roofing products, roll roofing products, membranes, adhesives, pipe coatings, hydraulic products, paving mixes, channel, ditch and pond coverings, dam and bridge protections, hydrophobic paints, electrical cable joint protections, oil and gas pipeline joints, seal filling compounds, sound insulation products, reinforcing and underlay felts, lower protections for Portiand cement-based concrete coatings and the like.

18. Bituminous product comprising at least one bituminous composition according to any one of Claims 1 to 14.

19. A bituminous product according to claim 18, which is an impervious product and preferably an impermeable product selected from roofing, waterproofing and other waterproofing products, asphalted shingles, roofing products based on polymer-modified bitumen, roll roofing products, membranes, adhesives, pipe coatings, hydraulic products, paving mixes, channel, ditch and pond coatings, dam protections and bridges, hydrophobic paints, electrical cable joint protections, oil and gas pipeline joints, joint fillers, sound insulation products, reinforcing and underlay felts, protections lower for Portiand cement-based concrete coatings and the like.