COMPOSITION COMPRISING ONE OR MORE PARTICULAR ADDITIVES

Abstract

Provided is a composition including at least one bitumen and at least one additive as defined herein. The composition provides emulsions of all types of bitumens, which can be used in the production of cold-poured mixes, having an improved internal strength and a rapid increase in cohesion.

Claims

1. A composition comprising at least one bitumen and at least one additive chosen from the compounds of formula (I) below or the compounds of formula (II) below: ##STR00004## wherein: R.sub.1 and R.sub.2, which may be identical or different, represent, independently of one another, a group chosen from a hydrogen atom, a group -(A1).sub.q1-S(O).sub.2OR.sub.8, a group (A2).sub.q2-P(O)(OR.sub.9).sub.2 and a group -(A3).sub.q3-C(O)OR.sub.10, R.sub.8, R.sub.9 and R.sub.10, which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C.sub.1-C.sub.22 alkyl radical, A1, A2 and A3, which may be identical or different, represent, independently of one another, a linear or branched C.sub.1-C.sub.4 alkylene radical, q1, q2 and q3, which may be identical or different, represent, independently of one another, an integer equal to 0 or 1, or R.sub.1 and R.sub.2 form, with the carbon atoms to which they are attached, a heterocycle comprising 5 ring members, wherein R.sub.1 and R.sub.2 do not simultaneously represent a hydrogen atom; R.sub.3 represents a hydrogen atom or a linear or branched, saturated or unsaturated C.sub.1-C.sub.22 alkyl radical; R.sub.4 and R.sub.5, which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C.sub.1-C.sub.22 alkyl radical; R.sub.6 and R.sub.7, which may be identical or different, represent, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated C.sub.1-C.sub.4 alkyl radical; D represents a hydrogen atom or a linear or branched, saturated or unsaturated C.sub.1-C.sub.22 alkyl radical; G represents a linear or branched, saturated or unsaturated C.sub.1-C.sub.22 alkylene radical; p is an integer equal to 0 or 1.

2. The composition as claimed in claim 1, wherein R.sub.1 and R.sub.2 form, with the carbon atoms to which they are attached, the group of formula (III) below: ##STR00005##

3. The composition as claimed in claim 1, wherein R.sub.3 denotes the hydrogen atom.

4. The composition as claimed in claim 1, wherein R.sub.4 and R.sub.5 simultaneously represent a hydrogen atom.

5. The composition as claimed in claim 1, wherein R.sub.6 and R.sub.7, which may be identical or different, represent, independently of one another, the hydrogen atom, the methyl radical or the ethyl radical.

6. The composition as claimed in claim 1, wherein said additive of formula (I), or formula (II), is chosen from 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-carboxy-6-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxy-5-methyl-4-hexyl-2-cyclohexene-1-octanoic acid, 6-carboxy-6-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxy-5-methyl-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-sulfo-4-hexyl-2-cyclohexene-1-octanoic acid, 5-sulfo-4-hexyl-2-cyclohexene-1-octanoic acid, 6-sulfo-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-sulfo-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 6-phosphono-4-hexyl-2-cyclohexene-1-octanoic acid, 5-phosphono-4-hexyl-2-cyclohexene-1-octanoic acid, 6-phosphono-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-phosphono-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof; 5,6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, 5,6-carboxy-4-pentyl-2-cyclohexene-1-nonanoic acid, 5-carboxylic anhydride-4-hexyl-2-cyclohexene-1-octanoic acid, 5-carboxylic anhydride-4-pentyl-2-cyclohexene-1-nonanoic acid, and mixtures thereof.

7. The composition as claimed in claim 1, wherein the amount of said additive of formula (I), or of formula (II), represents from 0.1% to 5% by weight, relative to the total weight of the composition.

8. A bituminous emulsion comprising at least one bitumen, at least one additive of formula (I) or of formula (II), as defined in claim 1, and at least one aqueous phase optionally containing at least one surfactant.

9. The bituminous emulsion as claimed in claim 8, wherein the amount of additive of formula (I) or of formula (II) represents from 0.1% to 5% by weight, relative to the total weight of the emulsion.

10. A process for producing a bituminous emulsion as defined in claim 8, comprising at least one step of mixing: at least one additive of formula (I), or formula (II) a bitumen, and an aqueous phase optionally containing at least one surfactant.

11. The process as claimed in claim 10, comprising the following successive steps: mixing said additive of formula (I), or formula (II), and a bitumen; then mixing an aqueous phase optionally containing at least one surfactant and the solution obtained at the end of the mixing of the bitumen and said additive.

12. The process as claimed in claim 10, comprising the following successive steps: mixing said additive of formula (I), or formula (II), and an aqueous phase optionally containing at least one surfactant; then mixing the solution obtained at the end of the mixing of the aqueous phase and of said additive, with the bitumen.

13. A cold-poured mix comprising at least one emulsion as defined in claim 8 and aggregates.

14. (canceled)

15. A method of producing a cold-poured mix as defined in claim 13, comprising combining the emulsion and the aggregates.

Description

EXAMPLES

Example 1

1. Preparation of Three Bituminous Emulsions

[0120] Three bituminous emulsions are produced with an emulsification pilot of the Emulbitume brand name, equipped with a colloid mill of Atomix C type.

[0121] The three bituminous emulsions contain 60% by weight of bitumen, having a 70/100 penetrability, originating from the Total Grandpuits refinery, relative to the total weight of the emulsion.

[0122] The coating emulsions prepared are slow coating emulsions of C60B6 type according to the standard NF EN 13808 of August 2013.

[0123] The aqueous phase is prepared by mixing: [0124] 25 g of emulsifier of fatty alkylamidopolyamine type having the name Polyram L920 sold by the company CECA S.A.; [0125] 1947 g of water; [0126] 28 g of 32% hydrochloric acid.

[0127] The composition of the three bituminous emulsions is indicated in table 1 below (the percentages are expressed relative to the total weight of the emulsion):

TABLE-US-00001 TABLE 1 Emulsion 1 Emulsion 2 Emulsion 3 Emulsion type (comp.) (comp.) (inv.) bitumen (% by weight) 60 60 60 aqueous phase (% by weight) qs qs qs Pripol 1017 Polymerized 0.6 fatty acid (% by weight) Cecabase FC + Additive 0.6 (% by weight)

[0128] The additive Cecabase FC+ comprises 45% by weight of oleic acid and 55% by weight of a mixture comprising 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid and 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid.

[0129] The polymerized fatty acid Pripol 1017 comprises, according to the technical sheet from the supplier Croda, approximately 2% by weight of fatty acid monomer, 78% by weight of fatty acid dimer and 20% by weight of fatty acid trimer.

[0130] The additives (the polymerized fatty acid Pripol 1017 for emulsion 2, and the additive Cecabase FC+ for emulsion 3) are introduced into the hot bitumen, heated to approximately 140 C., with stirring. The mixture is left to stir for 15 minutes for homogenization before emulsification.

[0131] The emulsification is carried out in a standard manner, with an Emulbitume pilot operating continuously at the flow rate of 60 liters/h. The bitumen/aqueous phase mixture at the weight ratio of 60/40 is introduced into an Atomix C by means of two separate circuits fed by two pumps.

2. Preparation of Three Cold-Poured Mixes

[0132] Three cold-poured mixes are prepared from the three bituminous emulsions mentioned above.

[0133] The three mixes were prepared with aggregates originating from Piasek quarry in Poland. The granular mixture is a mixture of 50% by weight of aggregates of 0-2 cm particle-size class and 50% by weight of aggregates of 2-8 cm particle-size class.

[0134] The amount of water added to the dry aggregates varies from 7 to 8 g and is adjusted according to the system so as to maintain a kneading time of around 10010 seconds.

[0135] In the present examples, the term kneading time is intended to mean the time during which the mixture comprising the aggregates, the cement, the water and the emulsion remains fluid with stirring.

[0136] The composition of the three cold-poured mixes is indicated in table 2 below:

TABLE-US-00002 TABLE 2 Mix 1 Mix 2 Mix 3 Mix type (comp.) (comp.) (inv.) Emulsion 1 (g) 12 Emulsion 2 (g) 12 Emulsion 3 (g) 12 Granular mixture (g) 100 100 100 Cement (CEM II) 1 1 1 Water (g) 7 8 8

3. Evaluation of the Internal Strength of the Three Cold-Poured Mixes

[0137] The internal cohesion of each of the three mixes is evaluated by means of the HCT test, Hilt Cohesion Test, described in the IDRRIM [Institute for Roads, Streets and Infrastructures for Mobility] guide on Matriaux Bitumineux Couls a Froid [Cold-Poured Bituminous Materials], (2015).

[0138] This test makes it possible to evaluate the tensile strength and flexural strength of the mix tested.

[0139] Test specimens of cold-poured mixes (CPMs), also known as CPBMs (Cold-Poured Bituminous Materials) 12012015 mm in size are produced by pouring 400 g of cold-poured mix into a 120120 mm mold with removable edges. After the mix has set, the edges of the mold are carefully removed and the test specimen is left to mature at ambient temperature for a given time (in this case 2 h).

[0140] The test was carried out on a table, the principle being to place half of the test specimen under vacuum while the other half is kept on a support. The test specimen is positioned at the edge of the table on a plastic support in two equal parts not fixed together. A counterweight is placed on the part which remains on the table. The other half of the test specimen is slipped over the vacuum, and the support under this part is removed.

[0141] The time required to break the mix after half of the test specimen has been placed above the vacuum is then measured. The result (in seconds) represents the HCT cohesion value after a defined maturing time, under known temperature and hygrometry conditions. The longer the time (under equivalent maturing conditions), the stronger the cold-poured mix and thus the more advanced the increase in cohesion.

[0142] The results for breaking time after two hours of maturing at 20 C. that were obtained on the cold-poured mixes produced from the three emulsions are presented in table 3 below:

TABLE-US-00003 TABLE 3 Mix 1 Mix 2 Mix 3 Mix type (comp.) (comp.) (inv.) Breaking time (seconds) 5 180 260

[0143] The breaking time of mix 3 according to the invention is significantly longer than the breaking time of the other two mixes.

[0144] A mix comprising the additive of formula (I) according to the invention thus has a very high cohesion after two hours of maturing, better than that obtained for a mix without additive or a mix comprising an additive described in the prior art, such as a polymerized fatty acid.

Example 2

1. Preparation of Three Bituminous Emulsions

[0145] Three bituminous emulsions are produced with an emulsification pilot of the Emulbitume brand name, equipped with a colloid mill of Atomix C type.

[0146] The three bituminous emulsions contain 60% by weight of bitumen, having a 70/100 penetrability, originating from the Total Gonfreville refinery, relative to the total weight of the emulsion.

[0147] The coating emulsions prepared are slow coating emulsions of C60B6 type according to the standard NF EN 13808 of August 2013.

[0148] The amount of emulsifier in the emulsion is 8 kg/t of a tallow polyamine having the trade name Polyram S, and 8 kg/t of a co-emulsifier of quaternary ammonium type sold under the name Stabiram MS8 by the company CECA S.A.

[0149] The pH of the aqueous phase was adjusted to 2 with 32% hydrochloric acid.

[0150] The composition of the three bituminous emulsions is indicated in table 4 below (the percentages are expressed relative to the total weight of the emulsion):

TABLE-US-00004 TABLE 4 Emulsion 4 Emulsion 5 Emulsion 6 Emulsion type (comp.) (inv.) (inv.) Bitumen (% by weight) 60 60 60 aqueous phase (% by weight) qs qs qs Cecabase FC + Additive 0.6 0.6 (% by weight) Introduction of the the bitumem the aqueous Cecabase FC + additive phase into

[0151] During the preparation of emulsion 5 according to the invention, the Cecabase FC+ additive is introduced into the hot bitumen, heated to approximately 140 C., with stirring. The mixture is left to stir for 15 minutes for homogenization before emulsification.

[0152] The aqueous phase is prepared at 40 C. by mixing the tallow polyamine Polyram S, the co-emulsifier Stabiram MS8, and the hydrochloric acid.

[0153] During the preparation of emulsion 6 according to the invention, the Cecabase FC+additive is introduced into the aqueous phase, prepared by mixing the tallow polyamine Polyram S, the co-emulsifier Stabiram MS8, and the hydrochloric acid.

[0154] The bitumen is heated to approximately 140 C. before emulsification.

[0155] In any event, the emulsification is carried out in a standard manner, with an Emulbitume pilot operating continuously at the flow rate of 60 liters/h. The bitumen/aqueous phase mixture at the weight ratio of 60/40 is introduced into an Atomix C by means of two separate circuits fed by two pumps.

2. Preparation of Four Cold-Poured Mixes

[0156] The four mixes were prepared with siliceous aggregates originating from the Vignat quarry. The granular mixture is a mixture of 50% by weight of aggregates of 0-2 cm particle-size class and 50% by weight of aggregates of 2-6 cm particle-size class.

[0157] The amount of water added to the dry aggregates varies from 9 to 10 g and is adjusted according to the system so as to maintain a kneading time of around 9010 seconds.

[0158] Mix 4 (comparative) is prepared from emulsion 4.

[0159] Mix 5 (comparative) is prepared from emulsion 4, and 0.6% by weight of Cecabase FC+ was added to the aggregate pre-wetting water in the form of a 10% suspension in water.

[0160] Mix 6 according to the invention is prepared from emulsion 5. Mix 7 according to the invention is prepared from emulsion 6.

[0161] The composition of the four cold-poured mixes is indicated in table 5 below:

TABLE-US-00005 TABLE 5 Mix 4 Mix 5 Mix 6 Mix 7 Mix type (comp.) (comp.) (inv.) (inv.) Emulsion 4 (g) 12 Emulsion 4 (g) 12 Emulsion 5 (g) 12 Emulsion 6 (g) 12 Cecabase FC + Additive** 0.6 (% by weight) Granular mixture (g) 100 100 100 100 Cement (CEM II) (g) 0.5 0.5 0.5 0.5 Water (g) 9 9 10 9 **The additive was introduced into the aggregate pre-wetting water, as indicated above.

3. Evaluation of the Increase in Cohesion of the Four Cold-Poured Mixes

[0162] The increase in cohesion of each of the four mixes is evaluated by means of a Benedict cohesion tester according to the standard ASTM D3910 (1998). The aggregates, the cement, the introduced water and the emulsion are mixed with a spatula for 40 seconds. The mixture is poured into a mold, as described in the standard, on a bituminous support. After breaking of the emulsion, the mold is carefully removed, and the test specimen thus produced is left to mature at ambient temperature. The resistive torque of the test specimens is measured with the cohesion tester at regular intervals. The higher the torque, the better the cohesion of the mix.

[0163] This test makes it possible to determine a time to reopening the road to traffic by measuring the maturing time required to obtain a threshold torque value. It is generally accepted by those skilled in the art that opening the road to traffic is possible at about a value of 20 kg.cm.

[0164] The torques are measured at regular intervals for a period of 90 minutes of maturing at 20 C. The results are presented in table 6 below:

TABLE-US-00006 TABLE 6 Mix 4 Mix 5 Mix 6 Mix 7 Mix type (comp.) (comp.) (inv.) (inv.) Torque (in kg .Math. cm) after 10 12 16 15 15 minutes Torque (in kg .Math. cm) after 16 18 20 20 30 minutes Torque (in kg .Math. cm) after 19 20 22 21 60 minutes Torque (in kg .Math. cm) after 21 22 24 22 90 minutes

[0165] Thus, mixes 6 and 7, comprising the additive of formula (I) according to the invention, have a torque of 20 kg.cm after only 30 minutes of maturing. In particular, mix 6, comprising emulsion 5 which was prepared by introducing the additive of formula (I) into the bitumen, gives the best results.

[0166] The results thus clearly indicate that the use of the additive of formula (I) according to the invention makes it possible to shorten the time to opening the road to traffic by at least 30 minutes, compared with the solutions known from the prior art.