Binder that is solid at room temperature

Abstract

A binder composition includes at least: a binder base selected among an oil, a bitumen base, a pitch, a clear binder, or mixtures thereof; an acid compound of general formula (I): R—(COOH).sub.z (I); an amide compound of general formula (II): R′—(NH).sub.nCONH—(X).sub.m—(NHCO).sub.p(NH).sub.n—R″ (II), the compounds of formula (I) and formula (II) being provided in a weight ratio of 10:1 to 1:16. A process for manufacturing bituminous mixes including at least the binder composition and aggregates, includes at least the steps of: heating the aggregates to a temperature ranging from 100° C. to 180° C., mixing the aggregates with the binder composition, and obtaining bituminous mixes. A method for transporting and/or storing and/or handling the binder composition includes transporting and/or storing and/or handling the binder composition in the form of blocks or pellets.

Claims

1. A binder composition comprising at least: a binder base selected from the group consisting of an oil, a bitumen base, a pitch, a clear binder, and mixtures thereof, an acid compound of general formula (I):
R—(COOH).sub.z  (I) wherein R represents a linear or branched, saturated or unsaturated chain comprising from 4 to 68 carbon atoms and z is an integer ranging from 2 to 4, and an amide an amide compound of general formula (II):
R′—(NH).sub.nCONH—(X).sub.m—(NHCO)p(NH).sub.n—R″  (II) wherein: the R′ and R″ groups, which may be identical or different, represent a saturated or unsaturated and linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms which optionally comprises heteroatoms, C.sub.5-C.sub.24 hydrocarbon-based rings and/or C.sub.4-C.sub.24 hydrocarbon-based heterocycles comprising one or more heteroatoms, and R″ may be H; the X group represents a saturated or unsaturated and linear, cyclic or branched hydrocarbon-based chain comprising from 1 to 22 carbon atoms which is optionally substituted and which optionally comprises heteroatoms, C.sub.5-C.sub.24 hydrocarbon-based rings and/or C.sub.4-C.sub.24 hydrocarbon-based heterocycles comprising one or more heteroatoms, n, m and p are integers having a value of 0 or 1, independently of one another, the composition comprises between 0.1% and 5% by weight of the acid compound, relative to a total weight of the binder composition, and between 0.1% and 5% by weight of the amide compound, relative to the total weight of the binder composition, and the acid compound and the amide compound are present in an acid compound:amide compound weight ratio ranging from 10:1 to 1:16, said binder composition being in a form that is solid under cold conditions and divided.

2. The binder composition as claimed in claim 1, wherein the acid compound and the amide compound are present in a weight ratio ranging from 5:1 to 1:9.

3. The binder composition as claimed in claim 1, wherein the acid compound is a diacid of general formula HOOC—C.sub.wH.sub.2w—COOH, wherein w is an integer varying from 4 to 22.

4. The binder composition as claimed in claim 1, wherein the amide compound is chosen from those of formula (IIA):
R′—CONH—(X).sub.m—NHCO—R″  (IIA) wherein: the R′ and R″ groups, which may be identical or different, represent a saturated or unsaturated and linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms which optionally comprises heteroatoms, C.sub.5-C.sub.24 hydrocarbon-based rings and/or C.sub.4-C.sub.24 hydrocarbon-based heterocycles comprising one or more heteroatoms; the X group represents a saturated or unsaturated and linear, cyclic or branched hydrocarbon-based chain comprising from 1 to 22 carbon atoms which is optionally substituted and which optionally comprises heteroatoms, C.sub.5-C.sub.24 hydrocarbon-based rings and/or C.sub.4-C.sub.24 hydrocarbon-based heterocycles comprising one or more heteroatoms; m is an integer having a value of 0 or 1.

5. The binder composition as claimed in claim 1, wherein the amide compound is chosen from those of formula (IIB):
R′—CONH—R″  (IIB) wherein: the R′ and R″ groups, which may be identical or different, represent a saturated or unsaturated and linear, branched or cyclic hydrocarbon-based chain comprising from 1 to 22 carbon atoms which optionally comprises heteroatoms, C.sub.5-C.sub.24 hydrocarbon-based rings and/or C.sub.4-C.sub.24 hydrocarbon-based heterocycles comprising one or more heteroatoms.

6. The binder composition as claimed in claim 1, wherein the amide compound is chosen from: hydrazides; diamides; and monoamides.

7. The binder composition as claimed in claim 6, wherein the amide compound is chosen from hydrazide selected from the group consisting of: C.sub.5H.sub.11—CONH—NHCO—C.sub.5H.sub.11, C.sub.9H.sub.19—CONH—NHCO—C.sub.9H.sub.19, C.sub.11H.sub.23—CONH—NHCO—C.sub.11H.sub.23, C.sub.17H.sub.35—CONH—NHCO—C.sub.17H.sub.35, or C.sub.21H.sub.43—CONH—NHCO—C.sub.21H.sub.43.

8. The binder composition as claimed in claim 6, wherein the amide compound is chosen from diamides selected from the group consisting of: N,N′-ethylenedi(laurylamide) of formula C.sub.11H.sub.23—CONH—CH.sub.2—CH.sub.2—NHCO—C.sub.11H.sub.23, N,N′-ethylenedi(myristylamide) of formula C.sub.13H.sub.27—CONH—CH.sub.2—CH.sub.2—NHCO—C.sub.13H.sub.27, N,N′-ethylenedi(palmitamide) of formula C.sub.15H.sub.31—CONH—CH.sub.2—CH.sub.2—NHCO—C.sub.15H.sub.31, N,N′-ethylenedi(stearamide) of formula C.sub.17H.sub.35—CONH—CH.sub.2—CH.sub.2—NHCO—C.sub.17H.sub.35.

9. The binder composition as claimed in claim 8, wherein the amide compound is N,N′-ethylenedi(stearamide) of formula C.sub.17H.sub.35—CONH—CH.sub.2—CH.sub.2—NHCO—C.sub.17H.sub.35.

10. The binder composition as claimed in claim 4, wherein the amide compound is chosen from monoamides selected from the group consisting of: laurylamide of formula C.sub.11H.sub.23—CONH.sub.2, myristylamide of formula C.sub.13H.sub.27—CONH.sub.2, palmitamide of formula C.sub.15H.sub.31—CONH.sub.2, stearamide of formula C.sub.17H.sub.35—CONH.sub.2.

11. The binder composition as claimed in claim 1, wherein it is prepared by bringing into contact: at least one binder base chosen from oils, bitumen bases, pitches, clear binders or mixtures thereof, between 0.1% and 5% by weight, by weight of the acid compound, relative to a total weight of the binder composition, between 0.1% and 5% by weight, of the amide compound, relative to the total weight of the binder composition, optionally between 0.5% and 20% by weight, of at least one anticaking agent, relative to the total weight of the binder composition, a weight ratio of the acid compound to the relative to the total weight of the binder composition, a weight ratio of the acid compound to the amide compound being from 10:1 to 1:16.

12. The binder composition as claimed in claim 1, which is in the form of bitumen block or bitumen pellets.

13. A bituminous composition comprising a binder composition as claimed in claim 1 and which further comprises aggregates and/or fillers.

14. The binder composition of claim 1, which is a bituminous mix and which comprises aggregates and optionally mineral and/or synthetic fillers.

15. A process for manufacturing bituminous mixes comprising at least the binder composition as claimed in claim 1 and aggregates, this process comprising at least the steps of: heating the aggregates to a temperature ranging from 100° C. to 180° C., mixing the aggregates with the binder composition as claimed in claim 1, obtaining bituminous mixes.

16. The process as claimed in claim 15, which does not comprise a step of heating the binder composition before it is mixed with the aggregates.

17. The bituminous composition of claim 13, which is a bituminous mastic and which comprises fillers.

Description

FIGURES

(1) FIG. 1: graphic representation of irreversible creep compliance divided by the stress (along the ordinate in kPa.sup.−1) of bituminous mastic compositions M1, M3, M5 and M7 after a creep-recovery cycle as a function of the stress (along the abscissa in Pa) Legend:

(2) .circle-solid.=M1; .square-solid.=M3; .box-tangle-solidup.=M5; X=M7

(3) FIG. 2: graphic representation of irreversible creep compliance divided by the stress (along the ordinate in kPa.sup.−1) of bituminous mastic compositions M2, M4, M6 and M8 after a creep-recovery cycle as a function of the stress (along the abscissa in Pa) .circle-solid.=M2; .square-solid.=M4; .box-tangle-solidup.=M6; X=M8

(4) FIG. 3: graphic representation of the complex modulus G* (along the ordinate in Pa) of bituminous mastic compositions M1, M3, M5 and M7, measured at 60° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s)

(5) Legend:

(6) .circle-solid.=M1; .square-solid.=M3; .box-tangle-solidup.=M5; X=M7

(7) FIG. 4: graphic representation of the complex modulus G* (along the ordinate in Pa) of bituminous mastic compositions M2, M4, M6 and M8, measured at 60° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s)

(8) .circle-solid.=M2; .square-solid.=M4; .box-tangle-solidup.=M6; X=M8

(9) FIG. 5: graphic representation of the complex modulus G* (along the ordinate in Pa) of bituminous mastic compositions M1, M3, M5 and M7, measured at 15° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s) Legend:

(10) .circle-solid.=M1; .square-solid.=M3; .box-tangle-solidup.=M5; X=M7

(11) FIG. 6: graphic representation of the complex modulus G* (along the ordinate in Pa) of bituminous mastic compositions M2, M4, M6 and M8, measured at 15° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s)

(12) .circle-solid.=M2; .square-solid.=M4; .box-tangle-solidup.=M6; X=M8

(13) FIG. 7: graphic representation of irreversible creep compliance divided by the stress (along the ordinate in kPa.sup.−1) of bituminous binder compositions C.sub.9, C.sub.10, C.sub.11 and C12 after a creep-recovery cycle as a function of the stress (along the abscissa in Pa)

(14) Legend:

(15) .circle-solid.═C9; .square-solid.═C10; .box-tangle-solidup.═C11; X═C12

(16) FIG. 8: graphic representation of the complex modulus G* (along the ordinate in Pa) of compositions C9, C10, C11 and C12, measured at 60° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s)

(17) Legend:

(18) .circle-solid.═C9; .square-solid.═C10; .box-tangle-solidup.═C11; X═C12

(19) FIG. 9: graphic representation of the complex modulus G* (along the ordinate in Pa) of compositions C9, C10, C11 and C12, measured at 15° C. and at a frequency of between 0.1 and 100 Hz (along the abscissa, the angular frequency expressed in rad/s)

(20) Legend:

(21) .circle-solid.═C9; .square-solid.═C10; .box-tangle-solidup.═C11; X═C12

EXPERIMENTAL SECTION

(22) Materials and Methods

(23) The properties of the binders are measured by means of the methods described below: Needle penetrability at 25° C. (P25): units= 1/10 mm, standard EN 1426 Ring and ball softening point (RBSP): units=° C., standard EN 1427 Dynamic viscosity (V Dyn): NF EN 13702, measured at temperatures of 100° C., 110° C., 120° C., 130° C., 140° C., 160° C., 180° C., 200° C. Resistance under load according to the standard NFT66 002: a texture analyzer model TAXT2 was used by the company Ametek at 35° C. or at 50° C. V=1 mm/min on 10 mm of depression.

(24) The maximum force and the force are measured at 10 mm in Newtons (N).

(25) The resistance at the maximum force and at 10 mm in Newtons per millimeter (N/mm) is evaluated.

(26) Complex modulus G* of the bituminous mastic composition measured at 15° C. and 60° C. and at a frequency of between 0.1 and 100 Hz: unit=MPa or Pa, EN 14770 standard. The test was performed using an oscillating shear rheometer (Model: Anton Paar). The results are reported as a function of the angular frequency expressed in rad/s.

(27) Multiple Stress Creep Recovery Test (MSCRT) measurement, measured according to the standard NF EN 16659. The test was carried out using a DSR dynamic shear rheometer in creep mode at a temperature of 60° C. The irreversible creep compliance was measured, that is to say the residual deformation of a test specimen after a creep-recovery cycle divided by the applied stress.

(28) Starting Materials:

(29) Bitumen base (B): Several bitumen bases, the characteristics of which are presented below, were used: a bitumen base of 35/50 grade, denoted B.sub.1, having a penetrability P.sub.25 of 41 1/10 mm and an RBSP of 52° C. and commercially available from the Total group under the brand name Azalt®; a bitumen base of 50/70 grade, denoted B.sub.2, having a penetrability P.sub.25 of 58 1/10 mm and an RBSP of 49.6° C. and commercially available from the Total group under the brand name Azalt®; a bitumen base of 35/50 grade, denoted B.sub.3, having a penetrability P.sub.25 of 37 1/10 mm and an RBSP of 52° C. and commercially available from the Total group under the brand name Azalt®;

(30) Additive: Additive A1 of formula (I): sebacic acid Additive A2 of formula (II): N,N′-ethylenedi(stearamide) sold by the company Croda under the name Crodawax 140®

(31) Fillers: mineral fillers of diameter less than or equal to 0.063 mm

(32) I— Formulation of Bituminous Binders:

(33) I-1. Compositions:

(34) The bitumen base (B.sub.1, B.sub.2 or B.sub.3) is introduced into a reactor maintained at 160° C. with stirring at 300 rpm for two hours. The additive(s) are then introduced into the reactor. The contents of the reactor are maintained at 160° C. with stirring at 300 rpm for 1 hour.

(35) Compositions C2 to C8 and C10 to C12 are prepared by bringing the bitumen base into contact with the additives, according to tables 1 and 2 below. The amounts are expressed as percentage by weight of additive compound relative to the total weight of the composition. Compositions C1 to C3 and C9 to C11 are comparative, compositions C4 to C8 and C12 are according to the invention.

(36) TABLE-US-00001 TABLE 1 content of the compositions C1 to C8 C1 C2 C3 C4 C5 C6 C7 C8 Bitumen base B1 B1 B1 B1 B1 B1 B1 B2 A1 — 1.5% — 1.5% 1% 1.5% 0.5% 1.5% A2 — — 3.5% 3.5% 3% 2.5%   4% 2.5%

(37) TABLE-US-00002 TABLE 2 content of the compositions C9 to C12 C9 C10 C11 C12 Bitumen base B3 B3 B3 B3 A1 — 1.5% — 1.5% A2 — — 2.5% 2.5%

(38) I-2. Preparation of the Solid Binder Pellets

(39) A. General Method for Preparing the Binder Cores of the Pellets According to the invention

(40) The binder composition is reheated at 160° C. for two hours in an oven before being poured into a silicone mold exhibiting different holes of spherical shape, so as to form the solid binder cores. After having observed the solidification of the binder in the mold, the surplus is leveled off using a blade heated with a Bunsen burner. After 30 minutes, the solid binder in the form of uncoated pellets is removed from the mold and stored in a tray covered with silicone paper. The binder cores are then allowed to cool to ambient temperature for 10 to 15 minutes.

(41) B. General Method for the Preparation of the Bitumen Cores of the Pellets According to the Invention with an Industrial Process

(42) For the implementation of this method, use may be made of a device and of a process as described in great detail in U.S. Pat. No. 4,279,579. Various models of this device are commercially available from the company Sandvik under the trade name Rotoform®.

(43) Bitumen pellets can also be obtained from the bituminous composition according to the invention poured into the tank of such a device and maintained at a temperature of between 130 and 160° C.

(44) An injection nozzle or several injection nozzles make(s) possible the transfer of the bitumen composition according to the invention inside the double pelletizing drum comprising an external rotating drum, the two drums being equipped with slots, nozzles and orifices making possible the pelletizing of bitumen drops through the first stationary drum and orifices exhibiting a diameter of between 2 and 8 mm of the external rotating drum. The bitumen drops are deposited on the upper face of a horizontal conveyor belt driven by rollers.

(45) Bitumen pellets were obtained respectively from the bituminous compositions C6 and C8 poured into the tank of such a device and maintained at a temperature of between 80 and 100° C.

(46) An injection nozzle or several injection nozzles make(s) possible the respective transfer of the bitumen compositions C6 and C8 inside the double pelletizing drum comprising an external rotating drum, the two drums being equipped with slots, nozzles and orifices making possible the pelletizing of bitumen drops through the first stationary drum and orifices exhibiting a diameter of between 2 and 8 mm of the external rotating drum. The bitumen drops are deposited on the upper face of a horizontal conveyor belt driven by rollers.

(47) I-3. Results:

(48) The results of the measurements of the properties of the bitumen compositions are set out in tables 3 and 4 below.

(49) TABLE-US-00003 TABLE 3 Properties of compositions C1 to C8 C1 C2 C3 C4 C5 C6 C7 C8 P25 39 20 28 20 19 21 23 20 ( 1/10 mm) RBSP (° C.) 53 104 106 108 106 105 105 105.5 V Dyn 120° C. 1.85 1.67 1.34 1.23 — 1.39 1.29 — V Dyn 130° C. 1.02 0.916 0.769 0.7 — 0.79 0.736 — V Dyn 140° C. 0.602 0.532 0.46 0.421 — 0.475 0.445 — V Dyn 160° C. 0.251 0.212 0.198 0.183 — 0.2 0.189 — V Dyn 180° C. 0.119 0.101 0.102 0.091 — 0.095 0.093 — V Dyn 200° C. 0.063 0.061 0.058 0.052 — 0.058 0.050 — Force Max a 35° C. 3.2 34.3 12.4 102 92 101 57.5 — Force at 10 mm at 3.2 32 12.4 100 90 101 57.5 — 35° C. Resistance at Max 9 233 66 568 475 566 388 — Force at 35° C. Resistance at 10 mm 9 260 66 790 727 855 424 — at 35° C. Max Force at 50° C. — — — — — 41 — 38 Resistance at Max — — — — — 98 — 53 Force at 50° C. Resistance at 10 mm — — — — — 337 — 302 at 50° C.

(50) It is found that compositions C4, C5, C6, C7 and C8 have, at ambient temperature, mechanical properties very significantly greater than those of comparative compositions C1 to C3, without their viscosity under hot conditions being strongly degraded (increased).

(51) TABLE-US-00004 TABLE 4 Properties of compositions C9 to C12 C9 C10 C11 C12 P25 ( 1/10 mm) 37 26 33 20 RBSP (° C.) 52 103 93 102 V Dyn 140° C. 0.747 0.468 0.428 0.349 V Dyn 160° C. 0.253 0.192 0.179 0.159 V Dyn 180° C. 0.113 0.091 0.086 0.079

(52) It is found that composition C12 according to the invention has a lower viscosity under hot conditions than those of comparative compositions C9 to C11.

(53) Complex Modulus G*

(54) It was demonstrated that composition C12 according to the invention has a complex modulus G* greater than the complex modulus of comparative compositions C9 to C11, whatever the frequency at which the complex modulus G* is measured over the operating temperature range of between 15 and 60° C.

(55) The complex modulus G* in particular reflects the mechanical strength of the compositions; it is therefore demonstrated that composition C12 according to the invention has a better mechanical strength compared to the comparative compositions.

(56) Multiple Stress Creep Recovery Test (MSCRT) Measurement

(57) It was demonstrated that composition C12 according to the invention exhibits an irreversible creep compliance (Jnr) lower than the irreversible creep compliance of comparative compositions C9 to C11, whatever the cumulative shear stress at which the irreversible creep compliance is measured, at an operating temperature of 60° C.

(58) The irreversible creep compliance reflects in particular the resistance of the composition to permanent deformation; it is therefore demonstrated that composition C12 according to the invention has a better resistance to permanent deformation compared to comparative compositions C9 to C11.

(59) As a result, the compositions according to the invention have mechanical properties that are superior to those of the comparative compositions without their viscosity under hot conditions being degraded (increased).

(60) II-Bituminous Mastic Formulation:

(61) II-1. Compositions:

(62) The bitumen base B.sub.1 is introduced into a reactor maintained at 160° C. with stirring at 300 rpm for two hours. The additive(s) are then introduced into the reactor. The contents of the reactor are maintained at 160° C. with stirring at 300 rpm for 1 hour. Compositions M1 to M8 are prepared by bringing the bitumen base B.sub.1 into contact with the additives A1 and A2, according to table 5 below. The amounts are expressed as percentage by weight of additive compound relative to the total weight of the supplemented bitumen base.

(63) The fillers are then introduced, in an amount of 30% or 50% by weight relative to the total weight of the composition (i.e. 70% or 50% by weight of supplemented bitumen base relative to the total weight of the mastic composition). The mineral filler and the bitumen were heated in an oven at 160° C. for 2 hours. The filler was then slowly added to the bitumen and the whole mixture was mixed at 160° C. The rotational speed was gradually increased in proportion to the increase in the density of material. The addition of the fillers was completed in approximately 20 minutes, and the mixing process was continued for 30 minutes in order to avoid load segregation.

(64) Compositions M1 to M6 are comparative, compositions M7 and M8 are according to the invention.

(65) TABLE-US-00005 TABLE 5 content of the compositions M1 to M8 M1 M2 M3 M4 M5 M6 M7 M8 Bitumen base B1 B1 B1 B1 B1 B1 B1 B1 A1 — — 1.5%  1.5%  — — 1.5% 1.5% A2 — — — — 2.5% 2.5%  2.5% 2.5% Supplemented 70% 50% 70% 50% 70% 50%  70%  50% bitumen base Filler 30% 50% 30% 50% 30% 50%  30%  50%

(66) I-2. Results:

(67) The results of the measurements of the properties of the bituminous mastic compositions are set out in table 6 below.

(68) TABLE-US-00006 TABLE 6 Properties of compositions M1 to M8 M1 M2 M3 M4 M5 M6 M7 M8 P25 30 23 21 17 25 19 19 15 ( 1/10 mm) RBSP (° C.) 54.6 61.6 104 87 99.5 102 105 100.5 Texture at 6.39 19.40 37.10 45.50 14.90 35.90 94.20 90.00 35° C. Texture at 0.93 2.47 12.00 14.20 5.39 10.40 31.30 36.3 50° C. V Dyn 3.246 7.061 2.878 7.94505 2.240 — 2.053 5.876 120° C. V Dyn 1.038 2.157 0.923 2.62 0.756 — 0.700 2.026 130° C. V Dyn 0.417 0.722 0.375 1.050 0.317 — 0.288 0.851 140° C. V Dyn 0.174 0.453 0.178 0.468 0.156 — 0.139 0.415 160° C.

(69) Complex Modulus G*

(70) It was demonstrated that the mastics according to the invention comprising 30% by weight or 50% by weight of filler exhibit a complex modulus G* greater than the complex modulus of the comparative compositions of mastics, whatever the frequency with which the complex modulus G* is measured, over the operating temperature range of between 15° C. and 60° C.

(71) The complex modulus G* in particular reflects the mechanical strength of the mastics; it is therefore demonstrated that the mastics according to the invention have a better mechanical strength compared to comparative compositions of mastics.

(72) Multiple Stress Creep Recovery Test (MSCRT) Measurement

(73) It was demonstrated that the mastics according to the invention comprising 30% by weight or 50% by weight of filler exhibit an irreversible creep compliance (Jnr) lower than the irreversible creep compliance of the comparative compositions of mastics, regardless of the cumulative shear stress at which the irreversible creep compliance is measured, at a working temperature of 60° C.

(74) The irreversible creep compliance in particular reflects the resistance of the mastics to permanent deformation; it is therefore demonstrated that the mastics according to the invention have a better resistance to permanent deformation compared to comparative compositions of mastics.

(75) As a result, the mastics according to the invention have mechanical properties that are superior to those of the comparative compositions of mastics without their viscosity under hot conditions being degraded (increased).