FORMULATION FOR BITUMEN EMULSION

Abstract

A formulation comprising at least one lignosulfonate, at least one nitrogenous surfactant, and at least one alkoxylated cationic compatibiliser is described in addition to bitumen emulsions produced from said formulation.

Claims

1. A formulation comprising: a) at least one nitrogenous cationic surfactant bearing at least one optionally quaternized fatty chain, and including from 0 to 5, limits inclusive, alkoxylated units; b) at least one alkoxylated cationic compatibilizer, including from 5 to 25, limits exclusive, alkoxylated units; and c) at least one lignosulfonate.

2. The formulation as claimed in claim 1, wherein said at least one nitrogenous surfactant a) is chosen from amine surfactants of fatty amine or alkylamidoamine or alkylimidazoline type and mixtures thereof, including up to 5 alkoxylated units and comprising at least one linear or branched, saturated or unsaturated hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive.

3. The formulation as claimed in claim 1, wherein said at least one nitrogenous surfactant a) is chosen from: i) an optionally alkoxylated fatty monoamine of formula (I) below: ##STR00007## wherein: R.sub.1 represents a saturated or unsaturated, linear or branched hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive, R.sub.2 and R.sub.3, which may be identical or different, are chosen from a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical, including from 1 to 4 carbon atoms, and an alkoxylated unit (CH.sub.2CHR.sub.4O).sub.hH, wherein R.sub.4 represents a hydrogen atom or a methyl or ethyl radical, h being a number ranging from 1 to 5, limits inclusive, where when h is greater than 1, the groups R.sub.4 may be identical or different; ii) an optionally alkoxylated fatty polyamine of formula (II) below: ##STR00008## wherein: R.sub.5 represents a saturated or unsaturated, linear or branched hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive, R.sub.6, R.sub.7 and R.sub.8, which may be identical or different, are chosen from a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical, including 1 to 4 carbon atoms, and an alkoxylated unit (CH.sub.2CHR.sub.9O).sub.iH, wherein R.sub.9 represents a hydrogen atom or a methyl or ethyl radical, i being a number ranging from 1 to 5, wherein when h is greater than 1, the groups R.sub.9 may be identical or different; m denotes a number chosen from 1, 2, 3, 4, 5 and 6 wherein when m is greater than 1, the groups R.sub.8 may be identical or different, n denotes a number chosen from 1, 2, 3, 4, 5 and 6; and iii) an optionally alkoxylated fatty amidoamine, of formula (Ma) below or the optionally alkoxylated cyclized equivalent thereof, of formula (IIIb) below: ##STR00009## wherein: the groups R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as defined, p and q are chosen from 1, 2, 3, 4, 5 and 6, s denotes an integer between 1 and 10, limits inclusive, t denotes an integer between 0 and 9, limits inclusive, wherein when s and t are strictly greater than 1, the groups R.sub.8 may be identical or different.

4. The formulation as claimed in claim 1, wherein said at least one alkoxylated cationic compatibilizer b) is chosen from fatty-chain amines, fatty-chain alkylamidoamines, fatty-chain alkylimidazolines, quaternized derivatives of said amines, alkylamidoamines and alkylimidazolines, and mixtures thereof, said at least one compatibilizer b) including from 5 to 25, limits exclusive, alkoxylated units and comprises at least one linear or branched, saturated or unsaturated hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive.

5. The formulation as claimed in claim 1, wherein said at least one alkoxylated cationic compatibilizer b) is chosen from: i) an alkoxylated fatty monoamine of formula (I) below: ##STR00010## wherein R.sub.1 represents a saturated or unsaturated, linear or branched hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive, R.sub.2 and R.sub.3, which may be identical or different, represent, independently of each other, an alkoxylated unit (CH.sub.2CHR.sub.4O).sub.jH, wherein R.sub.4 represents a hydrogen atom or a methyl or ethyl radical, j representing the total number of alkoxylated units per mole of compound of formula (I) and being a number ranging from 5 to 25, limits exclusive, wherein the groups R.sup.1.sub.4 may be identical or different; ii) an alkoxylated fatty polyamine of formula (II) below: ##STR00011## wherein R.sub.5 represents a saturated or unsaturated, linear or branched hydrocarbon-based chain, including from 8 to 30 carbon atoms, limits inclusive, R.sub.6, R.sub.7 and R.sub.8, which may be identical or different, represent an alkoxylated unit (CH.sub.2CHR.sub.9O).sub.jH, wherein R.sub.9 represents a hydrogen atom or a methyl or ethyl radical, j representing the total number of alkoxylated units per mole of compound of formula (II) and being a number ranging from 5 to 25, limits exclusive, wherein the groups R.sub.9 may be identical or different; m denotes a number chosen from 1, 2, 3, 4, 5 and 6, wherein when m is greater than 1, the groups Ws may be identical or different, n denotes a number chosen from 1, 2, 3, 4, 5 and 6; and iii) an alkoxylated fatty amidoamine, of formula (IIIa) below or the cyclized equivalent thereof of formula (IIIb) below: ##STR00012## wherein the groups R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as defined previously, p and q are chosen from 1, 2, 3, 4, 5 and 6, s denotes an integer between 1 and 10, limits inclusive, t denotes an integer between 0 and 9 limits inclusive, wherein when s and t are greater than 1, the groups R.sub.8 may be identical or different.

6. The formulation as claimed in claim 1, wherein said at least one alkoxylated cationic compatibilizer b) is chosen from: fatty amines and polyamines based on coconut, tallow or palm, ethoxylated with between 5 and 25 equivalents per mole, methyl chloride-quaternized derivatives of fatty amines and polyamines based on coconut, tallow or palm, and including in total from 5 to 25 (limits exclusive) ethoxylated units per mole, ethoxylated derivatives (total ethoxylated units between 5 and 25 per mole, limits exclusive) of mixtures of fatty alkylamidopolyamine and of fatty alkylimidazopolyamines obtained by reaction of fatty acids or of plant or animal oils such as coconut, tallow, palm, pine (or tall oil) fatty acids, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lauric, myristic, cetylic, stearic, oleic, arachidic or behenic acid with polyethylene polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), aminoethylpiperazine (AEP), pentaethylenehexamine (PEHA), dimethylaminopropylamine (DMAPA) and dimethylaminopropylaminopropylamine (DMAPAPA).

7. The formulation as claimed in claim 1, wherein component a) and/or component b) of the formulation may be present in quaternized form.

8. The formulation as claimed in claim 1, wherein component c) is a lignosulfonate chosen from sodium, calcium, magnesium or ammonium lignosulfonates.

9. The formulation as claimed in claim 1, wherein component c) is a lignosulfonate with a weight-average molar mass (Mw) of between 1 kg.Math.mol.sup.1 and 35 kg.Math.mol.sup.1, limits inclusive.

10. The formulation as claimed in claim 1, wherein the component b)/component c) weight ratio is between 0.1 and 4, limits inclusive, and the component a)/component b) weight ratio is between 0.1 and 2, limits inclusive.

11. The use of a formulation as claimed in claim 1, as a surfactant for the preparation of a bitumen emulsion.

12. The use as claimed in claim 11, wherein the formulation is present in a dose of between 0.1% and 5%, by weight of formulation, limits inclusive, relative to the total weight of the bitumen emulsion.

13. A process for preparing a bitumen emulsion from a formulation as claimed in claim 1, said process comprising: at least one step of mixing at least one bitumen, at least one said formulation and water, an optional step of acidification of the medium so as to obtain a pH value of less than 7, said process being performed at a temperature between ambient temperature and 160 C.

14. A bitumen emulsion substantially obtained according to the process of claim 13.

15. The use of a bitumen emulsion as claimed in claim 14 for preparing surfacing mixes, semi-warm surfacing mixes, cold-laid surfacing mixes, gravel emulsions (structuring or reprofiling gravel emulsions), cold-laid bituminous concretes, dense, semi-dense or open storable surfacing mixes, for making tack coats, for stabilizing grounds and impregnation works, cold-in-place recycling, for preparing coatings, optionally in combination with one or more other additives and/or fillers, for preparing sealing coatings.

Description

EXAMPLES

[0084] In order to test them, various formulations are prepared from lignosulfonates of diverse origin and of diverse properties.

[0085] The lignosulfonates used are presented in Table 1 below:

TABLE-US-00001 TABLE 1 Supplier Lignosulfonate M.sub.w (kg .Math. mol.sup.1) Borregaard Vanisperse CB 12.920 Tembec Arbo BL 15.735 Tembec GSA 16.210

[0086] The weight-average molar masses (M.sub.w) are determined by size exclusion chromatography, using a three-column system:

first column: Waters Ultrahydrogel Linear, 3007.8 mm,
second and third columns: Waters Ultrahydrogel 120 , 3007.8 mm.

[0087] For this determination, the injection flow rate is set at 0.8 mL.Math.min.sup.1, the detector temperature is 45 C., the temperature of the columns is 60 C. and the injection concentration is 5 mg.Math.mL.sup.1. The standards used are supplied by the company Agilent under the name PL EasiVial-PEG/PEO (PL2080-0200).

[0088] Five soaps (noted S1 to S5) are prepared by mixing the amount of formulation required to obtain the targeted dosage in the emulsion and water at 45 C. The pH of the soap is then adjusted to 2 with hydrochloric acid (Aldrich at 32% in water). The properties of the five soaps are collated in table 2 below, in which the amounts of components a), b) and c) are expressed as weight percentages relative to the total weight of the soap, and the amount of water added is the quantity sufficient for 100% by weight.

TABLE-US-00002 TABLE 2 Soap Component a) Component b) Lignosulfonate c)* S1 CecaBase 3860 (0.5%) Dinoramox S12 (1%) Vaniperse CB (1%) S2 CecaBase 3860 (0.5%) Dinoramox S12 (1%) Arbo BL (1%) S3 CecaBase 3860 (0.5%) Dinoramox S12 (1%) GSA (1%) S4 Dinoram SLB (0.5%) Dinoramox S12 (1%) Vaniperse CB (1%) S5 CecaBase 3860 (0.5%) Inipol CX15 at (1%) Vaniperse CB (1%) *Expressed as weight of solids

[0089] Slow emulsions according to the standard NF EN 13808 are manufactured with the aid of a laboratory group from the company EmulBitume (http://www.emulbiturne.com) equipped with an Atomix C colloidal mill. The mass content of bitumen is 60%. The bitumen used is a paraffinic bitumen with a penetrability of 160/220, sold by the company Total and originating from the Feyzin refinery (Rhne, France). The temperature of the bitumen during the preparation of the emulsion is 140 C.

[0090] The emulsions prepared from soaps S1 to S5 are numbered E1 to E5, respectively.

[0091] Another emulsion, emulsion E6, is produced with soap S1: the mass content of bitumen is 55%. The bitumen used is a paraffinic bitumen with a penetrability of 70/100, sold by the company Total. This bitumen is fluxed to 10% before making the emulsion. The fluxing agent used is sold by the company VWR under the reference Kerdane-light distillate for petroleum product testing.

Example 1

[0092] The results of characterization of the main properties of these emulsions E1 to E5 are characterized by a sedimentation stability test according to the standard EN12847 and by a cement test (percentage of material retained on a screen) according to the standard EN12848, and are collated in table 3 below:

TABLE-US-00003 TABLE 3 Recommendations E1 E2 E3 E4 E5 Stability D-S (%) <5% <5% <5% <5% <5% <5% Cement test <2% <2% <2% <2% <2% <2%

[0093] These first tests demonstrate that all emulsions comprising a formulation according to the present invention are stable and pass the cement test.

Example 2: Coating Quality Tests

[0094] Ten (10) different surfacing mixes are prepared using the five emulsions E1 to E5 produced previously and with two different qualities of aggregates G1 and G2. Aggregate G1 is a Veze basalt (France, Massif Central region), with a particle size distribution: 45% by weight of 0/4 mm, 20% by weight of 4/6 mm and 35% by weight of 6/10 mm). Aggregate G2 is a Sirolaise limestone (France, South-East region), with a particle size distribution: 40% by weight of 0/4 mm, 20% by weight of 4/6 mm and 40% by weight of 6/14 mm).

[0095] The surfacing mixes are prepared from the emulsions described above by mixing with the aggregates G1 and G2, according to the techniques well known to those skilled in the art. These surfacing mixes are then evaluated according to various criteria:

[0096] The coating quality is performed and evaluated according to the standard NF P98-257-1. For the grading after 2 hours (t0+2), in order to better represent the terrain phenomena and notably the resistance to ravelling on reworking, the surfacing mix is first stored in a pile, and then, at the time of observation, worked with a metal spatula for 30 seconds before spreading it and performing the grading.

[0097] The mechanical strength R and the water resistance r/R are evaluated according to the standard NF P98-251-4. The results are presented in Table 4 below:

TABLE-US-00004 TABLE 4 Recommendations E1 E2 E3 E4 E5 Binder content >3.8 4.2 4.2 4.2 4.2 4.2 of the surfacing mix (weight %) Coating quality 100/90 100/100 100/100 100/90 100/100 G1 - (t0/t0 + 2) % Coating quality 100/100 100/90 100/90 100/100 100/100 G2 - (t0/t0 + 2) % R (MPa) - G1 >3.5 4.0 4.7 4.1 4.3 R (MPa) - G2 >3.5 7.3 7.5 7.2 6.5 r/R - G1 >0.55 0.63 0.65 0.69 0.65 r/R - G2 >0.55 0.64 0.65 0.66 0.69

[0098] The surfacing mixes prepared using the formulations according to the invention all have a good coating quality (percentage of coverage t0) and good resistance to ravelling on reworking (percentage of coverage t0+2). Similarly, all of the formulations meet the specifications as recommended by the standards in terms of mechanical strength (R) and water resistance (r/R).

Example 3: Impregnation Test

[0099] The impregnation test is performed according to the standard NF EN 12849:2009-08 with emulsion E6 described above, at ambient temperature. Emulsion E6 fully meets the criteria of the abovementioned standard insofar as it totally impregnates the sand in a time of less than 20 minutes, and the surface of the sand after impregnation is clearly recognized.