FLUXING AGENTS FOR HYDROCARBON BINDERS

Abstract

The invention relates to the use, as fluxing agent for bitumen compositions, of at least one compound having the formula (I)

R.sup.1C(O)OR.sup.2 (I) where: each of R.sup.1 and R.sup.2, which may be identical or different, is a linear or branched hydrocarbon chain which does not carry an unsaturated covalent bond, optionally interrupted by one or more oxygen atoms, and optionally carrying one or more hydroxyl functions.

Claims

1. Method for preparing a bituminous product comprising contacting solid mineral particles, a composition comprising a hydrocarbon binder and a compound of formula (I) or a mixture comprising at least one such compound of formula (I)
R.sup.1C(O)OR.sup.2 (I) where: each of R.sup.1 and R.sup.2, which may be identical or different, is a linear or branched hydrocarbon chain which does not carry an unsaturated covalent bond, optionally interrupted by one or more oxygen atoms, and optionally carrying one or more hydroxyl functions provided that, in the case of a mixture additionally comprising one or more unsaturated compounds of formula (II)
RC(O)OR(II) where: each of R and R, identical or different, is a linear or branched unsaturated hydrocarbon chain comprising at least one CC double bond, the mass ratio (II)/(I+II), defined as the ratio of the total mass of the unsaturated compounds of formula (II) to the sum of the total mass of the compounds of formula (I) and the total mass of the unsaturated compounds of formula (II), is less than 15% by mass, preferably less than 10% by mass.

2. Method according to claim 1, wherein the bituminous product is a surface dressing.

3. Method according to claim 1, wherein the hydrocarbon binder is used in the form of an anhydrous binder and comprises, based on the total weight of binder, from 3% to 18% by weight of said compound of formula (I).

4. Method according to claim 2, wherein the hydrocarbon binder is a binder emulsion and comprises, based on the total weight of the hydrocarbon binder, 0.1 to 10% by weight of said compound of formula (I).

5. Method according to claim 1, wherein the bituminous product is a bituminous concrete emulsion.

6. Method according to claim 5, wherein the hydrocarbon binder comprises 1 to 25% by weight of said compound of formula (I), based on the total weight of the hydrocarbon binder.

7. Method according to claim 1, wherein the bituminous product is a cold-mix bituminous material.

8. Method according to claim 7, wherein the hydrocarbon binder comprises, based on the total weight of the hydrocarbon binder, 0.1 to 6% by weight of said compound of formula (I).

9. Method according to claim 1, wherein the bituminous product is a hot-mix or warm-mix asphalt.

10. Method according to claim 9, wherein the hydrocarbon binder comprises 1 to 30% by weight of said compound of formula (I), based on the total weight of the hydrocarbon binder.

11. Method according to claim 1, wherein the bituminous product is a storable asphalt.

12. Method according to claim 1, wherein the compound of formula (I) has a molecular weight of 140 g/mol to 270 g/mol.

Description

EXAMPLES

Description of Test Methods:

[0170] Stabilization of fluxed binders: [0171] Anhydrous binders: This is a method of obtaining a thin layer of binder. Stabilization is carried out according to NF EN 13074 1.2 (April 2011) by leaving the bitumen fluxed for 24 hours at laboratory temperature, then transferred to a ventilated oven for 24 hours at 50 C., and finally 24 hours at 80 C. to allow the flux to evaporate. [0172] STV pseudo-viscosity: [0173] For anhydrous binders: This is a method of measuring the viscosity of a fluxed bitumen by determining the flow time of the product at 40 C. or 50 C. through a 10 mm orifice. STV pseudo-viscosity is measured according to NF EN 12846-2 (April 2011). [0174] Penetrability: Penetrability is the consistency expressed as the depth, in tenths of a millimetre, corresponding to the vertical penetration of a reference needle into a test sample of the material, under prescribed conditions of temperature, load and time of application of the load. The penetrability test is carried out according to standard NF EN 1426 (June 2007). In the examples, the measurements were taken at 25 C., for a load of 100 g and a duration of 5 s. Penetrability can be measured from a fluxed bitumen, a stabilized binder obtained from a fluxed bitumen or a [0175] Ball-ring temperature: This is the temperature at which the binder reaches a precise consistency under the reference conditions of the test. Two horizontal discs of bitumen, moulded in shouldered brass rings, are heated in a stirred liquid (water) bath with a controlled rate of temperature rise (5 C./min, initial bath temperature of (51) C.), while each supports a steel ball. The softening point noted will correspond to the average temperature at which the two discs soften sufficiently to allow each ball, wrapped with bituminous binder, to descend from a height of (25.00.4) mm. The measurement is carried out in accordance with standard NF EN 1427 (June 2007). The ball-ring temperature can be measured from a fluxed bitumen, a stabilized binder obtained from a fluxed bitumen or a stabilized binder obtained from a bitumen emulsion. [0176] Loss of mass after stabilization: The loss of mass after stabilization is measured as the difference in mass between the binder deposited at the beginning of the stabilization procedure and the binder mass actually measured after the stabilization step (standard NF EN 13074 1.2, April 2011). [0177] Evaporation curves (thermobalance): This is a measure of the loss of mass of a fluxed bitumen as a function of time at a fixed temperature of 85 C. The test is carried out using a thermobalance and allows the evaporation kinetics of a flux to be evaluated. [0178] Adhesivity: This is a method for determining the binder-aggregate adhesivity and the influence of additives on the characteristics of this adhesivity (Standard NF EN 12272-3, July 2003). The required amount of binder is heated to the spreading temperature and then applied evenly to a steel plate. The test is carried out at (51 C.). One hundred graded chippings are distributed over the binder and then rolled. The prepared plate is turned over and placed on a three-point support. A steel ball falls on the plate from a height of 500 mm, three times in 10 s. [0179] The compactability of an emulsion asphalt concrete is determined by the gyratory shear press compaction test (NF P 98-252June 1999): Compaction is obtained by kneading under low static compression a cylinder of hydrocarbon mix contained in a mould limited by pellets and maintained at a fixed temperature. Compaction is achieved by a combination of gyratory shear and an axial resultant force applied by a mechanical head. This method makes it possible to determine the evolution of the percentage of voids in the specimen as a function of the number of gyrations. [0180] BCE modulus (NF EN 12697-26 Annex CJune 2012): Prior to the measurement of the stiffness modulus, emulsion asphalt concrete specimens are prepared by press compaction at a voids content value equivalent to the voids content measured according to the Duriez modality 2 test by removing 2%. The specimens are then cured at 35 C. and 20% humidity for 14 days. The stiffness modulus is then measured at 14 days by indirect tension to cylindrical specimens conditioned at 10 C. (IT-CY). The rise time, measured from the start of the loading pulse and which is the time required for the application of the load to move from the initial contact loading to the maximum value, must be 1244 ms. [0181] BCE handling: This test is carried out 4 hours after the BCE has been manufactured with a NYNAS workability meter. It consists in measuring the force required by a mobile arm to move at constant speed about 10 kg of asphalt contained in a mould provided for this purpose. The workability of the asphalt is sufficient if the force is less than about 200 newtons. [0182] Duriez test, modality 1 (NF P 98-251-4, DATE): The purpose of this test method is to determine, for two compaction modalities, the percentage of voids and the water resistance, at 18 C., of a cold hydrocarbon mixture with bitumen emulsion from the ratio of the compressive strengths with and without immersion of the specimens. According to modality 1, the specimens are made with a load of 60 kN per specimen.

Description of the Compounds Tested:

[0183] The compounds tested are as follows:

[0184] F1 Isopropyl laurate

[0185] F2 mixture of methyl laurate and methyl myristate having the following characteristics: [0186] Vapour pressure: <0.55 Pa at 25 C. [0187] Flash point in closed cup: 141 C. [0188] Density at 20 C.: 867-870 g/cm.sup.3 [0189] Boiling interval: 261-295 C.

[0190] F3 Methyl cocoate

[0191] F4 Ethyl laurate

[0192] F5 Texanol with the following characteristics:

[0193] Vapour pressure: 1.3 Pa at 25 C.

[0194] Flash point in closed cup: 122 C.

[0195] Density at 20 C.: 946 g/cm.sup.3

[0196] Boiling interval: 255-261 C.

Example 1: Fluxed Binders for Surface Dressings

[0197] The following binders are prepared:

TABLE-US-00001 TABLE 1 T0 C1 L1 L2 L3 L4 L5 Bitumen Supplier ESSO Grade 70/100 Flux Name Ptrolier (1) F1 F2 F3 F4 F5 Content (% by 0 6.2 6 5.5 5.5 5.5 10 weight based on the weight of binder) Adhesive Name Impact 9000 (2) dope Content (% by 0 0.3 0.3 0.3 0.3 0.3 0 weight based on the weight of binder) (1) Greenflux SD marketed by TOTAL (2) Tallol fatty amides, N-[(dimethylamino)-3propyl] marketed by INGEVITY

[0198] Binder T0 is a non-flowable binder, which serves as a control for comparing the performance of the binder according to the invention to the binder without the addition of a compound according to the invention. Binder C1 is a fluxed binder with a volatile petroleum flux, which serves as a comparative example. Binders L1 and L2, L3, L4 and L5 are binders according to the invention.

[0199] The properties of the binders before/after stabilization and the adhesion results of the binders to the aggregates are shown in the following table:

TABLE-US-00002 TABLE 2 T0 C1 L1 L2 L3 L4 L5 Before stabilization STV pseudo- 440 429 450 481 484 341 viscosity 40 C., 10 mm, s Penetrability 85 at 25 C., 1/10 mm Ball-ring 45.4 temperature, C. After stabilization Loss of mass 3.0% 4.2% 3.6% 2.5% 3.7% after stabilization Penetrability 124 97 106 149 112 at 25 C., 1/10 mm Ball-ring 43.0 44.6 44.6 41.0 43.6 temperature, C. Adhesivity to the Vialit plate 5 C. + viadop PX10051 40 g/m.sup.2 La meilleraie 6/10 aggregates-washed dry Fallen 7 0 0 0 0 unstained Fallen 39 22 17 24 7 stained Glued to 54 78 83 76 93 the plate

[0200] The stabilization of fluxed bitumen is carried out according to the protocol described in the standard NF EN 13074 1.2 (April 2011). All tests are conducted according to the protocols described in the standards referenced and explained above. It can be seen that the binders according to the invention provide satisfactory results in terms of adhesivity and flowability (seen through the viscosity). In addition, the binders according to the invention regain their properties before fluxing, as seen through the penetrability and the ball-ring temperature. These results show that the binders according to the invention make it possible to obtain hard surface dressings in a short period of time, which allows a quick return to traffic.

[0201] Evaporation profiles (flux mass loss as a function of time) for binders C1, L1, L2, L3 and L4 without stabilization were measured. The evaporation profile of binder C2, having the same composition as binder C1 was also added, except that Greenflux SD was replaced by Oleoflux, a non-volatile non-petroleum flux. The results are reported in the following table:

TABLE-US-00003 TABLE 3 binder C2 L1 L2 L3 L4 C1 Sample mass (g) 4.71 4.09 4.83 5.08 5.4 4.47 Observations No odour No odour No odour No odour time (mm) Loss of mass (% flux) 0 0.0 0.0 0.0 0.0 0.0 0.0 1 2.4 1.2 1.1 1.5 1.3 1.5 2 3.7 2.0 1.8 1.5 1.6 1.8 5 7.9 3.7 4.5 3.3 3.6 2.1 10 13.1 7.0 7.1 5.6 6.4 2.6 22 20.5 11.3 12.7 9.6 11.8 2.6 30 24.7 15.8 16.5 12.5 16.2 2.9 60 37.7 26.8 26.7 20.4 26.5 3.2 90 44.5 35.8 32.7 27.3 34.7 5.5 127 51.8 42.3 38.4 31.8 41.5 7.6 181 60.6 47.7 43.6 36.2 47.1 10.2

[0202] It can be seen that in binders C1 and L1 to L4 the flux has volatilized but not in binder C2.

Example 2: Bituminous Concrete Emulsion

[0203] Bituminous concrete emulsions are prepared according to the following formulas:

TABLE-US-00004 TABLE 4 BCE I1 BCE I2 BCE I3 BCE C1 BCE C2 BCE C3 Solid mineral Uzerche 0/4 aggregates fraction Pagnac 4/6.3 Pagnac pre-lacquered 6/10 with 1.8 wt % emulsion Filler emulsion 7.1 wt % Flux-content 0.3 wt % 0 Flux-type F1 F2 F3 Oleoflux Greenflux SD Theoretical residual 5.0 wt % 5.0 wt % 5.0 wt % 5.3 wt % 5.0 wt % 5.0 wt % anhydrous binder content

TABLE-US-00005 TABLE 5 BCE I4 BCE I5 BCE C4 BCE C5 BCE C6 Solid mineral fraction Dussac 0/2 + Dussac 2/6 + Dussac 6/10 Filler emulsion 7.7 wt % Flux - content 0.3 wt % 0 Fluxing - type F4 F6 Oleoflux Greenflux SD Theoretical residual 5.0 wt % 5.0 wt % 5.3 wt % 5.0 wt % 5.0 wt % anhydrous binder content

[0204] In these two tables:

[0205] wt % means percentage by weight based on the weight of the solid mineral fraction. The pre-lacquer or filler emulsion is in both cases a cationic emulsion. In both cases, bitumen emulsions are used which contain a 70/100 bitumen as binder. In both cases bitumen emulsions with a binder content of 65% by weight, based on the total weight of the emulsion, are used.

[0206] The flux is introduced by spraying at the end of mixing.

[0207] The compactability (GC), modulus, workability and compressive strength of these emulsion asphalt concretes are evaluated.

[0208] The results for the Uzerche-Pagnac formulas are given in the following tables:

TABLE-US-00006 TABLE 6 GC % voids as a function of the number of gyrations 5 10 15 20 25 30 40 50 60 80 100 120 150 200 BCE I1 24.2 20.9 19.1 17.8 17 16.2 15.1 14.3 13.6 12.6 11.8 11.2 10.5 9.6 BCE I2 24.3 21 19.2 18 17.1 16.4 15.3 14.5 13.9 12.9 12.2 11.6 10.9 10 BCE I3 23.9 20.8 19.1 17.9 17 16.3 15.2 14.3 13.7 12.7 11.9 11.3 10.6 9.8 BCE C1 23.7 20.5 18.6 17.4 16.5 15.8 14.6 13.7 13.0 12.0 11.2 10.6 9.8 8.8 BCE C2 24.1 21.2 19.1 17.9 17 16.3 15.2 14.3 13.7 12.6 11.9 11.3 10.6 9.7 BCE C3 27.1 23.8 21.9 20.7 19.8 19.1 18 17.1 16.5 15.5 14.7 14.1 13.4 12.5

[0209] The compactability results demonstrate the ability of compound (I) to improve the compaction of emulsion asphalt concrete and to reduce void content compared with the same formula without fluxing (BCE C3).

TABLE-US-00007 TABLE 7 Modulus change (MPa) 10 C. 124 ms storage 35 C. 20% RH 3 days 7 days 14 days 21 days BCE I2 614 547 689 656 BCE I3 940 1127 1227 1322 BCE C1 252 455 491 578 BCE C2 820 1109 1313 1463 BCE C3 2483 3168 3349 3472

[0210] Compound (I) allows a good increase in consistency of the bituminous concrete emulsion compared with the reference formula BCE Cl.

TABLE-US-00008 TABLE 8 Workability (N) at 4 hours BCE I1 334 BCE I2 253 BCE I3 327 BCE C1 272 BCE C2 233 BCE C3 187

[0211] Compound (I) maintains an acceptable workability value

TABLE-US-00009 TABLE 9 Compressive strength Duriez - modality 1 % voids R (MPa) r/R BCE I1 9.3 2.22 0.79 BCE I2 7.4 2.03 0.75 BCE I3 8.1 2.49 0.94 BCE C1 9.2 2.67 0.8 BCE C2 8.8 2.64 0.84 BCE C3 10.3 6.18 0.89

[0212] Compound (I) maintains an acceptable value of compressive strength. The void content is similar to the measured value for the reference formulae Cl and C2 and lower than the measured value for the flux free formula C3.

[0213] The results for the Dussac formulas are given in the following tables:

TABLE-US-00010 TABLE 10 GC % voids as a function of the number of gyrations 5 10 15 20 25 30 40 50 60 80 100 120 150 200 BCE I4 26.1 23.1 21.5 20.3 19.5 18.9 17.9 17.2 16.6 15.7 15.1 14.6 14.0 13.3 BCE I5 25.9 23.0 21.3 20.3 19.4 18.8 17.8 17.1 16.6 15.8 15.2 14.7 14.2 13.6 BCE C4 25.9 22.8 21.1 20.0 19.1 18.4 17.5 16.7 16.1 15.3 14.6 14.1 13.6 12.9 BCE C5 26.3 23.5 21.8 20.8 19.9 19.3 18.4 17.7 17.1 16.3 15.7 15.2 14.6 14.0 BCE C6 27.6 24.7 23.1 21.9 21.1 20.5 19.4 18.7 18.1 17.3 16.6 16.1 15.5 14.8

[0214] The compactability results demonstrate the ability of compound (I) to improve the compaction of the bitumen concrete emulsion and to reduce void content compared with the same formula without flux (BCE C6).

TABLE-US-00011 TABLE 11 Workability (N) at 4 hours BCE I4 240 BCE I5 310 BCE C4 241 BCE C5 406 BCE C6 641

[0215] Compound (I) improves the workability of bituminous concrete emulsion compared with the reference solutions.

TABLE-US-00012 TABLE 12 10 C. 124 ms storage Module change (MPa) 35 C. 20% RH 3 days 7 days BCE I5 758 1274 BCE C4 644 836

[0216] Compound (I) allows a good rise in consistency of the bituminous concrete emulsion compared with the reference formula BCE C4.

TABLE-US-00013 TABLE 13 Compressive strength Duriez - modality 1 % voids R r/R BCE I4 9.7 1.94 0.92 BCE I5 9.5 2.24 0.91 BCE C4 10.1 2.44 0.89

[0217] Compound (I) is used to maintain an acceptable value of compressive strength. The void content is similar to the measured value for the reference formula C4.