EMULSIFYING COMPOSITION FOR SPREADING BITUMEN

Abstract

Provided is an aqueous acidic emulsifying composition comprising a specific amine and a polymerized fatty acid, a process for preparing the composition, a process for preparing bituminous emulsion and to the use of the composition for spreading bitumen.

Claims

1. An aqueous acidic emulsifying composition comprising: A) from 0.01 to 20% by weight, relative to the total weight of the aqueous composition, of at least one amine chosen from the amines of following formulae: i) an optionally alkoxylated fatty monoamine of following formula (I): ##STR00007## in which: R.sub.1 represents a saturated or unsaturated, linear or branched carbon chain comprising 8 to 24 carbon atoms, R.sub.2 and R.sub.3, which are identical or different, represent a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical comprising 1 to 4 carbon atoms, or a (CH.sub.2CHR.sub.4O).sub.hH group, with R.sub.4 representing a hydrogen atom, a methyl or ethyl radical, and h being an integer ranging from 1 to 10, wherein if h>1, there are several groups R.sub.4 which may be identical or different, ii) an optionally alkoxylated fatty polyamine of following formula (II): ##STR00008## in which: R.sub.5 represents a saturated or unsaturated, linear or branched carbon chain comprising 8 to 24 carbon atoms, R.sub.6, R.sub.7 and R.sub.8, which are identical or different, represent a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical comprising 1 to 4 carbon atoms, or a (CH.sub.2CHR.sub.9O).sub.iH group, with R.sub.9 representing a hydrogen atom, a methyl or ethyl radical, and i denoting an integer ranging from 1 to 10, wherein if i>1 there are several groups R.sub.9 as defined above and which may be identical or different m denotes an integer between 1 and 6, wherein if m>1 there are several groups R.sub.8 as defined above and which may be identical or different, n denotes an integer between 1 and 6, iii) an optionally alkoxylated fatty amidoamine of following formula (Ma) or the optionally alkoxylated cyclized equivalent thereof, of following formula (IIIb): ##STR00009## in which: the groups R.sub.5, R.sub.6, R.sub.7 and R.sub.8 have the same meaning as in the formula (II), p and q denote an integer between 1 and 6, s denotes an integer between 1 and 10, t denotes an integer between 0 and 9, wherein if s>1 or t>1, there are several groups R.sub.8 defined above and which may be identical or different, B) from 0.001% to 10% by weight, relative to the total weight of the aqueous composition, of at least one polymerized fatty acid having a molar mass greater than 350 g.Math.mol.sup.1 and an acid number greater than 160 mg KOH g.sup.1, according to standard ASTM D465 of 2005, C) less than 20% by weight, relative to the total weight of the aqueous composition, of at least one bitumen, and D) a water content greater than 5% by weight relative to the total weight of the aqueous composition.

2. The aqueous composition as claimed in claim 1, wherein the amines are chosen from octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, myristoleylamine, palmitoleylamine, oleylamine; fatty amines of coconut, palm, olein or tallow, myristyl dimethylamine, lauryl dimethylamine, oleyl dimethylamine, stearyl dimethylamine, tallow dimethylamine, coconut dimethylamine, palm dimethylamine; the corresponding diethylated or dipropylated derivatives, ethoxylated fatty amines of tallow, coconut, palm, olein, and also the propoxylated and butoxylated derivatives; N-coco-propylenediamine, N-stearyl propylenediamine, N-oleyl propylenediamine, N-tallow propylenediamine, N-soya propylenediamine, N-coco dipropylenetriamine, N-oleyl dipropylenetriamine, N-tallow propylenetriamine and N-tallow tripropylenetetramine; N,N,N-trimethyl-N-tallow propylenediamine and also the corresponding diethylated or dipropylated derivatives; ethoxylated fatty polyamines of tallow, coconut, palm, olein, and also the propoxylated and butoxylated derivatives; and mixtures thereof; dimethylaminopropylamine (DMAPA) or dimethylaminopropylaminopropylamine (DMAPAPA) and mixtures thereof.

3. The aqueous composition as claimed in claim 1, wherein the polymerized fatty acid is obtained by polymerization of at least one unsaturated fatty acid selected from crotonic acid (C4), isocrotonic acid (C4), undecylenic acid (C11), hypogeic acid (C16), palmitoleic acid (C16), oleic acid (C18), elaidic acid (C18), vaccenic acid (C18), petroselinic acid (C18), gadoleic acid (C20), gondoic acid (C20), cetoleic acid (C22), erucidic acid (C22), brassidic acid (C22), nervonic acid (C24), tiglic acid (C5), sorbic acid (C6), linoleic acid (C18), hiragonic acid (C16), linolenic acid (C18), -linolenic acid (C18), eleostearic acid (C18), parinaric acid (C18), homo--linolenic acid (C20), arachidonic acid (C20), clupanodonic acid (C22), taken alone or as mixtures.

4. The aqueous composition as claimed in claim 1, wherein the acid number of the polymerized fatty acid is between 160 mg KOH.Math.g.sup.1 and 320 mg KOH.Math.g.sup.1, according to standard ASTM D465 of 2005.

5. The aqueous composition as claimed in claim 1, wherein the composition comprises from 0.05% to 10% by weight of at least one amine of formula (I), and/or (II) and/or (IIIa) and/or (IIIb) defined above, relative to the total weight of the aqueous composition.

6. The aqueous composition as claimed in claim 1, wherein it comprises from 0.005% to 5% by weight of polymerized fatty acid, relative to the total weight of the aqueous composition.

7. The aqueous composition as claimed in claim 1, wherein the weight ratio between the amine(s) and the polymerized fatty acid(s) is between 90/10 and 10/90.

8. The aqueous composition as claimed in claim 1, wherein the pH thereof ranges from 0.5 to 5.

9. A process for preparing at least one bituminous emulsion comprising at least one step of mixing at least one composition as defined in claim 1 with a bitumen.

10. An anhydrous composition comprising: at least one amine as defined in claim 1, and at least one polymerized fatty acid as defined in claim 1.

11. The anhydrous composition as claimed in claim 10, wherein it comprises from 10% to 90% by weight of amine, relative to the total weight of the anhydrous composition.

12. The anhydrous composition as claimed in claim 10, wherein it comprises from 10% to 90% by weight of polymerized fatty acid, relative to the total weight of the anhydrous composition.

13. The anhydrous composition as claimed in claim 10, wherein the weight ratio between the amine(s) and the polymerized fatty acid(s) in the anhydrous composition is between 90/10 and 10/90.

14. A process for preparing an aqueous acidic emulsifying emulsion as defined in claim 1, comprising at least one step of mixing: at least one composition as defined in claim 10 with an aqueous phase.

15. The use of the aqueous acidic emulsifying composition as defined in claim 1 for preparing a bituminous spreading emulsion.

16. The use of the anhydrous composition as defined in claim 10 for preparing bituminous spreading emulsions.

Description

EXAMPLES

Example 1

1. Preparation of an Anhydrous Composition

[0140] In order to prepare 1 kg of an anhydrous composition according to the invention, 670 g of Dinoram S (tallow diamine, CAS No. 61791-55-7, sold by ARKEMA), melted beforehand at 60 C., are introduced into a round-bottomed flask. The diamine amine is stirred under an inert atmosphere and 330 g of Pripol 1017 (fatty acid dimer sold by CRODA) are added. A rise in viscosity is noted when approximately 70% of the pouring is reached. The mixture is subsequently maintained at 70 C. for one hour. It is emptied into a bottle after taking off samples for analysis. The product is a waxy solid when cold, which has a melting point around 25 C.

2. Preparation of Aqueous Compositions

[0141] In order to prepare 1 kg of an anhydrous composition according to the invention, 670 g of Dinoram S (tallow diamine, CAS No. 61791-55-7, sold by ARKEMA), melted beforehand at 60 C., are introduced into a round-bottomed flask. The diamine amine is stirred under an inert atmosphere and 330 g of Pripol 1017 (fatty acid dimer sold by CRODA) are added. A rise in viscosity is noted when approximately 70% of the pouring is reached. The mixture is subsequently maintained at 70 C. for one hour. It is emptied into a bottle after taking off samples for analysis. The product is a waxy solid when cold, which has a melting point around 25 C.

[0142] Aqueous compositions are prepared by mixing the amount of emulsifier as indicated in table 1 below with water heated to 45 C. The pH of the aqueous phases is adjusted to 2 by the addition of 32% hydrochloric acid.

[0143] The compositions A1 to A3 are comparative aqueous compositions, while the compositions A4 and A5 are aqueous compositions according to the invention. The contents are expressed in grams.

TABLE-US-00001 TABLE 1 A1 A2 A3 A4 A5 Amine (1) 2.3 2.3 2.3 2.3 Anhydrous composition 3.45 according to 1 Ex1 Capric acid 1.15 Oleic acid 1.15 Fatty acid (2) 1.15 Hydrochloric acid 2.1 2.3 1.9 1.9 1.9 Water (q.s. to) 100 100 100 100 100 (1) Dinoram S sold by ARKEMA is a tallow diamine of CAS No. 61791-55-7. (2) 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.

3. Preparation of the Bituminous Emulsions

[0144] The bitumen emulsions were obtained with a RINK ELEKTRO brand mill. The content by weight of bitumen is 60%. The bitumen used is a paraffinic bitumen with 70/100 penetrability, supplied by Total and originating from the Feyzin refinery in France. The temperature of the bitumen during the emulsification is 140 C.

[0145] To prepare the emulsions, the aqueous phase is introduced into the funnel of the mill before it is started. The aqueous phase is recirculated in the mill and the amount of bitumen necessary to obtain the desired concentration of bitumen is then gradually added to the recirculating aqueous phase. The total time of introduction of the bitumen is approximately 1 minute. The circuit is then drained and the emulsion recovered for analysis.

[0146] Table 2 below gives the contents of the components of the bituminous emulsions.

TABLE-US-00002 TABLE 2 B1 B2 B3 B4 B5 Aqueous phase A1 400 Aqueous phase A2 400 Aqueous phase A3 400 Aqueous phase A4 400 Aqueous phase A5 400 Bitumen 600 600 600 600 600

4. Evaluation of the Bituminous Emulsions

[0147] The emulsions are subsequently analyzed to determine their quality and their application properties.

[0148] The quality of the emulsion is assessed by the residue on 0.5 mm screens after manufacture (measured according to standard NF EN 1429 of December 1999) and the particle size analysis carried out using a Mastersizer 3000 particle size analyzer from Malvern.

[0149] The particle size analyzer is set up as follows: [0150] refractive index at 1.625 for the bitumen with an imaginary part at 0.002 and [0151] refractive index of 1.33 for the water.

[0152] The value given in table 3 as the median diameter of the emulsion corresponds to the value Dv (0.5) given by the apparatus, that is to say the maximum value of the diameter of the dispersed bitumen particles representing 50% of the volume of the emulsion.

Breaking Index

[0153] The quality of the destabilization after application is assessed using the breaking index measured with Sikaisol filler according to the procedure described in standard NF EN 13075-1 (September 2002).

[0154] The lower this index, the more the emulsion will tend to destabilize rapidly after application, leading to maturation and rapid reopening to traffic.

TABLE-US-00003 TABLE 3 B1 B2 B3 B4 B5 Retention on 0.5 mm <0.1 <0.1 <0.1 <0.1 <0.1 screen (weight %) Dv (0.5) m 5.3 5.0 6.0 5.3 5.2 Breaking index 120 5 123 5 118 5 90 5 89 5

[0155] It can be seen from these results that the addition of fatty acid with a constant amine dosage does not disrupt the quality of the emulsion (with the possible exception of oleic acid which slightly degrades the median diameter) but that only the polymerized fatty acid Pripol 1017 has a significant impact on the breaking index, indicating quicker destabilization under application conditions.

Example 2

1. Preparation of the Compositions

[0156] Aqueous compositions are prepared by mixing the amount of emulsifier as indicated in table 4 below with water heated to 45 C. The pH of these aqueous phases is adjusted to 2 by the addition of 32% hydrochloric acid.

[0157] Composition A6 is a comparative composition, while composition A7 is a composition according to the invention. The contents are expressed in grams.

TABLE-US-00004 TABLE 4 A6 A7 Amine (1) 2.3 2.3 Fatty acid (2) 1.15 Hydrochloric acid 2.7 2.7 Water (q.s. to) 100 100 (1) Dinoram S (sold by ARKEMA) is a tallow diamine of CAS No. 61791-55-7. (2) 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.

2. Preparation of the Bituminous Emulsions

[0158] Three bituminous emulsions are produced with an Emulbitume emulsification pilot fitted with a colloid mill of Atom ix C type. The bituminous emulsions contain 60% by weight of bitumen, with 70/100 penetrability, originating from Total's Feyzin refinery, relative to the total weight of the emulsion. The emulsification is carried out in a standard manner at the flow rate of 60 liters.Math.h.sup.1. The bitumen/aqueous phase mixture at the weight ratio (60/40) is introduced into the Atomix C by means of two separate circuits fed by two pumps. The temperature of the bitumen during the emulsification is 140 C.

[0159] For the emulsion B8, the aqueous phase used is the aqueous phase A6. The fatty acid is introduced into the bitumen, under hot conditions and with stirring (Rayneri) with a homogenization time of 15 minutes, according to the teaching of document EP0416682 from SHELL Internationale Research Maatschappij.

[0160] Table 5 below gives the contents of the components of the bituminous emulsions.

TABLE-US-00005 TABLE 5 B6 B7 B8 Aqueous phase A6 400 400 Aqueous phase A7 400 Fatty acid (3) 1.15 Bitumen 600 600 600 (3) 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.

3. Evaluation of the Bituminous Emulsions

[0161] The emulsions are subsequently analyzed to determine their quality and their application properties.

[0162] The quality of the emulsion is assessed by the residue on 0.5 mm screens after manufacture (measured according to standard NF EN 1429 of December 1999) and the particle size analysis carried out using a Mastersizer 3000 particle size analyzer from Malvern.

[0163] The particle size analyzer is set up as follows: [0164] refractive index at 1.625 for the bitumen with an imaginary part at 0.002 and [0165] refractive index of 1.33 for the water.

[0166] The value given in table 6 as the median diameter of the emulsion corresponds to the value Dv (0.5) given by the apparatus, that is to say the maximum value of the diameter of the dispersed bitumen particles representing 50% of the volume of the emulsion.

Breaking Index

[0167] The quality of the destabilization after application is assessed using the breaking index measured with Sikaisol filler according to the procedure described in standard NF EN 13075-1 (September 2002).

[0168] The lower this index, the more the emulsion will tend to destabilize rapidly after application, leading to maturation and rapid reopening to traffic.

TABLE-US-00006 TABLE 6 B6 B7 B8 Retention on 0.5 mm screen <0.1 <0.1 <0.1 (weight %) Dv (0.5) m 3.8 4.1 3.9 Breaking index 128 5 102 5 118 5

[0169] These results show that the combination of fatty acid and amine within an aqueous phase has a significant impact on the breaking index.

[0170] The comparison of the results for the emulsions B7 and B8 show that, when the acid is introduced into the aqueous phase (emulsion B7), and not into the bitumen (emulsion B8) as taught by the prior art, an even quicker destabilization is obtained.

[0171] These two examples show that the choice of the amine(s) and polymerized fatty acid(s), and also their mode of introduction into the bituminous emulsion, are critical for obtaining a good quality emulsion and leading to rapid destabilization under the conditions of application.