BITUMINOUS COMPOSITIONS COMPRISING AN AMINE ADDITIVE AND A HYDROXIDE, THEIR PREPARATION PROCESS AND APPLICATIONS

Abstract

The invention concerns bituminous compositions comprising: a bitumen, a hydroxide XOH, with X=Na, Ca, Mg, Li or K, and at least one amine additive selected from amines, diamines, polyamines, alkyl amido amines, amidopolyamines and imidazolines,
wherein said bituminous composition is substantially free of saponifiable and saponified carboxylic acids, meaning that, if present, the weight of saponifiable and saponified carboxylic acids represents at most 0.01% of the total weight of said bituminous composition
and the bitumen represents at least 60% by weight of said bituminous composition,
their preparation process and their use in road applications.

Claims

1. A bituminous composition comprising: a bitumen, a hydroxide XOH, with X=Na, Ca, Mg, Li or K, and at least one amine additive selected from amines, diamines, polyamines, alkyl amido amines, amidopolyamines and imidazolines, wherein said bituminous composition is substantially free of saponifiable and saponified carboxylic acids, meaning that, if present, the weight of saponifiable and saponified carboxylic acids represents at most 0.01% of the total weight of said bituminous composition, and the bitumen represents at least 60% by weight of said bituminous composition.

2. The bituminous composition according to claim 1, wherein the bitumen represents from 79 to 99.98% by weight, preferably from 86 to 99.98% by weight, and more preferentially from 90 to 99.9% and more preferentially from 92.8 to 99.8% by weight, of bitumen, of said bituminous composition.

3. The bituminous composition according to claim 1, wherein the amine additive represents at most 3% by weight, preferably from 0.01 to 2% by weight, and more preferentially from 0.05 to 1% by weight, and more preferentially from 0.1 to 0.5% by weight, of said bituminous composition.

4. The bituminous composition according to claim 1, wherein the hydroxide XOH with X=Na, Ca, Mg, Li or K represents at most 3% by weight, preferably from 0.01 to 2% by weight, and more preferentially from 0.05 to 1% by weight, and more preferentially from 0.1 to 0.7% by weight, of said bituminous composition.

5. The bituminous composition according to claim 1, wherein the amine additive is selected from: Amines of formula (I): ##STR00005## wherein: R is a saturated or unsaturated, substituted or unsubstituted, optionally branched or cyclic, hydrocarbon radical with 8 to 24 carbon atoms, for example derived from tallow fatty acids, or tall oil fatty acids; and R.sub.1 and R.sub.2 can be the same or different and are selected from hydrogen or hydrocarbon radical with 1 to 24 carbon atoms; R.sub.1 and R.sub.2 are preferably selected from hydrogen or methyl; Diamines and Polyamines of formula (II):
R—(NH-L).sub.n-NH.sub.2  (II) wherein: R has the same meaning as in (I) above, L represents a linear or branched hydrocarbon radical with 1 to 6 carbon atoms, for instance L is —(CH.sub.2).sub.m— with m=1, 2 or 3 and, n is an integer greater than or equal to 1, in particular n is an integer from 1 to 6; Alkyl Amido amines of formula (III): ##STR00006## wherein R, R.sub.1, R.sub.2 and L have the same meaning as in (I) and (II), above; Amidopolyamines of formula (IV) and Imidazolines:
RCO—(NH-L).sub.p-NH.sub.2  (IV) wherein R and L have the same meaning as in (I) and (II) above, and p is an integer greater than or equal to 1, in particular p is an integer from 1 to 10.

6. The bituminous composition according to claim 1, wherein the amine additive is selected from amines, diamines, polyamines, alkyl amido amines and amidopolyamines including a fatty chain.

7. The bituminous composition according to claim 1, wherein the amine additive is an amidopolyamine including a fatty chain of formula:
RCO—[NH-L].sub.p-NH.sub.2  (IV) where: p is an integer greater than or equal to 1, in particular p is an integer from 1 to 10, L is a linear or branched hydrocarbon radical with 1 to 6 carbon atoms, for instance L is —(CH.sub.2).sub.m— with m=1, 2 or 3, R is a saturated or unsaturated, substituted or unsubstituted, optionally branched hydrocarbon radical with 8 to 24 carbon atoms.

8. The bituminous composition according to claim 7 wherein the amine additive of the composition is a mixture of amidopolyamines of formula (IV) in which p is an integer from 1 to 10, L is —(CH.sub.2).sub.2—, and R are the hydrocarbon chains of the fatty acids of tall oil.

9. The bituminous composition according to claim 1, wherein the hydroxide XOH is selected from NaOH and KOH, and is preferably NaOH.

10. The bituminous composition according to claim 1, wherein said bituminous composition also comprises an olefinic polymer.

11. The bituminous composition according to claim 10 wherein the olefinic polymer is chosen among: (a) the copolymers of ethylene and glycidyl (meth) acrylate chosen from random and block copolymers, preferably statistic copolymers, of ethylene and a monomer selected from glycidyl acrylate and glycidyl methacrylate, comprising from 50% to 99.7% by weight, preferably from 60% to 95% by weight, more preferably from 60% to 90% by weight of ethylene; (b) the terpolymers of ethylene, monomer A and monomer B chosen from random and block terpolymers, preferably statistic terpolymers, of ethylene, a monomer A and a monomer B; the monomer A being selected from vinyl acetate, (C.sub.1-C.sub.6)alkylacrylates and (C.sub.1-C.sub.6)alkylmethacrylates and the monomer B being selected from glycidyl acrylate and glycidyl methacrylate; in particular, the terpolymers ethylene/monomer A/monomer B comprising from 0.5% to 40% by weight, preferably from 5 to 35% by weight, more preferably from 10% to 30% by weight of units resulting from monomer A and from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of units resulting from monomer B, the rest being formed by units derived from the ethylene; (c) the copolymers resulting from the grafting of a monomer B selected from glycidyl acrylate and glycidyl methacrylate, on a polymer substrate; in particular, the polymer substrate comprises a polymer selected from polyethylenes, especially low-density polyethylenes, polypropylenes, random or block copolymers, preferably statistic copolymers, of ethylene and vinyl acetate, random or block copolymer, preferably statistic copolymers, of ethylene and (C.sub.1-C.sub.6) alkylacrylate or (C.sub.1-C.sub.6)alkylmethacrylate; advantageously, the copolymers of ethylene and vinyl acetate or of ethylene and (C.sub.1-C.sub.6)alkylacrylate or (C.sub.1-C.sub.6)alkylmethacrylate comprise from 40% to 99.7% by weight, preferably from 50% to 99% by weight of ethylene; in particular, such grafted copolymers comprise from 0.5% to 15% by weight, preferably from 2.5% to 15% by weight of grafted units resulting from the monomer B.

12. The bituminous composition according to claim 1, wherein said bituminous composition also comprises an elastomer, preferably a crosslinked elastomer.

13. A process for the preparation of a bituminous composition according to claim 1, wherein the following components are mixed at a temperature in the range of 90 to 230° C., preferably of 120° to 200° C.: a bitumen, a hydroxide XOH with X=Na, Ca, Mg, Li or K and, an additive selected from amines, diamines, polyamines, alkyl amido amines, amidopolyamines and imidazolines.

14. The process according to claim 13 wherein an olefinic polymer and/or an elastomer, preferably a crosslinked elastomer, is(are) also mixed with the other components.

15. A use of a bituminous composition according to claim 1, in road applications, in particular for the manufacture of hot bituminous mixes, asphalts, surface coatings, materials for the construction and the maintenance of road foundations and their surfacing or for road works.

16. A method for improving the stability under solicitations of the penetrability at 25° C. measured according to EN 1426 and/or for improving the stability of the ring-and-ball softening temperature measured according to EN 1427 of a bituminous composition, comprising a bitumen and optionally an olefinic polymer and/or an elastomer, wherein the improvement is obtained by incorporation in the bituminous composition of a hydroxide XOH, with X=Na, Ca, Mg, Li or K and of an amine additive selected from amines, diamines, polyamines, alkyl amido amines, amidopolyamines and imidazolines, in particular as defined in claim, said bituminous composition being substantially free of saponifiable and saponified carboxylic acids, meaning that, if present, the weight of saponifiable and saponified carboxylic acids represents at most 0.01% of the total weight of said bituminous composition.

17. The method according to claim 16 wherein the conditions of solicitations are defined in EN 12607-1 or EN 14769.

18. A method for reducing the H.sub.2S emission or content of a bituminous composition, comprising a bitumen and optionally an olefinic polymer and/or an elastomer, wherein the reduction is obtained by incorporation in the bituminous composition of a hydroxide XOH, with X=Na, Ca, Mg, Li or K and of an amine additive selected from amines, diamines, polyamines, alkyl amido amines, amidopolyamines and imidazolines, in particular as defined in claim 5, said bituminous composition being substantially free of saponifiable and saponified carboxylic acids, meaning that, if present, the weight of saponifiable and saponified carboxylic acids represents at most 0.01% of the total weight of said bituminous composition.

Description

EXAMPLES

[0150] The needle penetrability was measured at 25° C. according to the standard DIN EN 1426 (Penetration at 25° C. in the Table).

[0151] The ring and ball softening temperature was measured according to the standard DIN EN 1427 (softening point (R+B) in the Table).

[0152] The resistance of the bituminous compositions against hardening and ageing was respectively tested according to the standards DIN EN 12607-1 and DIN 12607-1+14769.

[0153] The European Standard DIN EN 12607-1 specifies a method for measuring the combined effects of heat and air on a thin film of a bituminous composition in constant renewal. It simulates the hardening undergone by a bituminous composition during mixing before coating applications.

[0154] The European Standard DIN EN 12607-1+14769 specifies a method for accelerated long-term aging carried out in a pressure aging vessel (PAV).

[0155] The affinity between aggregates and the bituminous compositions was evaluated at 25° C. according to the standard DIN EN 12697-11. The rotation speed was 60 min.sup.−1 and the size and the type of the aggregates were respectively 8-11.2 mm Quartzite. The mean value of the bitumen coating expressed in % is presented in the Table.

[0156] The wheel tracking of the bitumen compositions was evaluated at 40° C. according to the standard DIN EN 12697-22.

[0157] Conditions: [0158] T=40° C. [0159] In air [0160] Solid rubber while [0161] 40 mm thickness weal [0162] AC 8 D N type of Asphalt

[0163] A bituminous composition according to the invention was prepared with:

[0164] A bitumen A with a Penetration measured at 25° C. according the standard DIN EN 1426 of 77 mm/10 and a softening point (R+B) measured according to the standard DIN EN 1427 of 46.8° C. (grade 70/100). [0165] A powder of NaOH 97% (Aldrich) or a powder of KOH 97% (Aldrich) [0166] An amine additive marketed by AkzoNobel under the name Wetfix BE (CAS 68910-93-0).

[0167] The preparation protocol was the following: [0168] Temperature of bitumen: 180° C. [0169] 0.5% w/w dried NaOH (Example 1) or KOH (Example 2) added and stirred for 3 hours, [0170] 0.2% w/w Wetfix BE added and stirred for ½ hour.

[0171] The bituminous compositions according to the invention and the same composition, but without NaOH or KOH and without the amine additive (Comparative Example), were tested. A bitumen B (AZALT), with a Penetration measured at 25° C. according the standard DIN EN 1426 of 58 mm/10 and a softening point (R+B) measured according to the standard DIN EN 1427 of 51° C. (grade 50/70), was also tested

[0172] The results are presented in the Table hereafter.

[0173] The results show that the combined use of NaOH or KOH and of the amine additive highly improved the resistance to hardening and ageing with respect to both needle penetrability at 25° C. and ring and ball softening temperature. The ageing is slowed down.

[0174] Additionally, the tests on the affinity between aggregates and the bitumen compositions show that the adhesive force of the bituminous composition is maintained. On the contrary, the adhesive force is totally lost in case of use of NaOH alone (results not shown).

[0175] In the wheel tracking test, the addition of NaOH or KOH and of the amine additive, in comparison with the bitumen A, shows a great improvement to crackings resistance.

TABLE-US-00001 TABLE Example 1 Example 2 according according Test Comparative to the to the Comparative Method example invention invention example Test, Unit DIN EN Bitumen A (NaOH) (KOH) Bitumen B Grade 70/100 50/70 50/70 50/70 Softening Point 1427 46.8 53.6 51.8 51 (R + B), ° C. Penetration at 1426 77 60 62 58 25° C., mm/10 Resistance to 12607-1 hardening RTFOT Softening Point 1427 52.2 56.4 54.8 58.4 (R + B), ° C. Increase of 1427 +5.4 +2.8 +3.0 +7.4 Softening Point (R + B), ° C. Penetration at 1426 47.7 48 50.8 39.4 25° C., mm/10 Retained 1426 62 80 82 68 Penetration, % Resistance to 12607-1 + long term ageing 14769 RTFOT + PAV Softening Point 1427 60.8 61.8 61 67.2 (R + B), ° C. Increase of 1427 +14 +8.2 +9.2 +16.2 Softening Point (R + B), ° C. Penetration at 1426 24.6 31.2 32.2 22.0 25° C., mm/10 Retained 1426 32 52 52 38 Penetration, % Mean value of the 12697- bitumen coating 11  6 h, % 60 55 50 55 24 h, % 35 35 35 35 48 h, % 30 25 20 30 Wheel Tracking 12697- 8.7 mm 1.8 mm 1.8 mm 2.0 mm 22