FLUIDIZING COMPOUNDS FOR HYDRAULIC COMPOSITIONS

Abstract

Disclosed is a compound with the following formula (I):

##STR00001## as well as the use thereof, in particular as a chelating agent of positively charged ions, or as a fluidizing agent for hydraulic compositions. Also disclosed is a hydraulic composition comprising a compound with formula (I), at least one hydraulic binder, at least one aggregate, and water.

Claims

1. A compound with the following formula (I): ##STR00018## wherein: M is chosen from the group consisting of H, alkaline and alkaline earth metals and .sup.+HNRR′ groups, R and R′ being chosen independently from each other from H, (C.sub.1-C.sub.3)alkyl, either linear or branched, and alcohols in C.sub.1-C.sub.3, either linear or branched; R.sub.1 is chosen from the group consisting of H, A.sub.1 and (C.sub.1-C.sub.4)alkyl groups, either linear or branched, when A is described by formula (1) below, or, where A is described by formula (2) or (3) below, R.sub.1 is chosen from the group consisting of H and (C.sub.1-C.sub.4)alkyl groups, either linear or branched; R.sub.2 is chosen from the group consisting of H, OM, M being as defined above and from (C.sub.1-C.sub.4) alkyl groups, either linear or branched; A stands for: a group A.sub.1 with the following formula (1): ##STR00019## wherein: n is an integer from 1 to 40; m is an integer from 1 to 40; and Z is chosen from the group consisting of: ′—CHR.sub.3—NH— groups, R.sub.3 being chosen from the group consisting of H, COOH and (C.sub.1-C.sub.6)alkyl groups, either linear or branched;  —C(═O)—NH— groups; and  —C(R.sub.5)═N— groups, where R.sub.5 is H or Me; a group A.sub.2 with the following formula (2): ##STR00020## wherein: n is an integer from 1 to 40; m is an integer from 1 to 40; r is 0 or an integer from 1 to 6; and M, R.sub.1 and R.sub.2 are as defined above in formula (I); a group A.sub.3 with the following formula (3): ##STR00021## wherein: n′ is an integer from 1 to 50; the sum of m′+p′ varies from 1 to 6; m′ is an integer from 1 to 5; p′ is an integer from 1 to 5; and M, R.sub.1 and R.sub.2 are as defined above in formula (I); Z is as defined above in formula (1).

2. The compound according to claim 1, having the following formula (II): ##STR00022## wherein: R.sub.1 is chosen from the group consisting of H and (C.sub.1-C.sub.4)alkyl groups, or stands for a group A.sub.1 with formula (1) as defined in claim 1; and M, R.sub.2, n, m are as defined in claim 1.

3. The compound with formula (II) according to claim 2, wherein: R.sub.2 is an OM group; n varies from 19 to 31; m varies from 3 to 10; and Z is chosen from the group consisting of: —CHR.sub.3—NH— groups, where R.sub.3 is chosen from the group consisting of H, COOH and (C.sub.1-C.sub.6)alkyl groups, either linear or branched; and —C(═O)—NH— groups.

4. The compound with formula (II) according to claim 3, wherein R.sub.1 is H or stands for a group A.sub.1 with formula (1).

5. The compound according to claim 1, having the following formula (III): ##STR00023## wherein: R.sub.1 is chosen from the group consisting of H and (C.sub.1-C.sub.4)alkyl groups; and M, R.sub.2, n, m and r are as defined in claim 1.

6. The compound with formula (III) according to claim 5, wherein R.sub.1 is H and R.sub.2 is an OM group and r is 0 or varies from 1 to 3.

7. The compound according to claim 1, described by the following formula (IV): ##STR00024## wherein: R.sub.1 is chosen from the group consisting of H and (C.sub.1-C.sub.4)alkyl groups; and M, R.sub.2, n′, m′ and p′ are as defined in claim 1.

8. The compound with formula (IV) according to claim 7, wherein: R.sub.1 is H; R.sub.2 is an OM group; and Z is chosen from the group consisting of: —CHR.sub.3—NH— groups, where R.sub.3 is chosen from the group consisting of H, COOH and (C.sub.1-C.sub.6)alkyl groups, either linear or branched; and —C(═O)—NH— groups.

9. A chelating agent of positively charged ions comprising a compound according to claim 1.

10. A hydraulic composition comprising: a compound according to claim 1, at least one hydraulic binder, at least one aggregate, and water.

11. A fluidizing agent for hydraulic compositions comprising a compound according to claim 1.

12. A admixture to hydraulic binders comprising a compound according to claim 1, alone or in combination with at least one plasticizer and/or superplasticizer.

13. A method to decrease the sensitivity to phyllosilicate clays of a hydraulic composition, comprising adding a compound according to claim 1 into said hydraulic composition.

14. A method to decrease the sensitivity to alkaline sulfates in solution of a hydraulic composition, comprising adding a compound according to claim 1 into said hydraulic composition.

15. A hydraulic composition comprising: the compound of claim 2, at least one hydraulic binder, at least one aggregate, and water.

16. A hydraulic composition comprising: the compound of claim 3, at least one hydraulic binder, at least one aggregate, and water.

17. A hydraulic composition comprising: the compound of claim 4, at least one hydraulic binder, at least one aggregate, and water.

18. A hydraulic composition comprising: the compound of claim 5, at least one hydraulic binder, at least one aggregate, and water.

19. A hydraulic composition comprising: the compound of claim 6, at least one hydraulic binder, at least one aggregate, and water.

20. A hydraulic composition comprising: the compound of claim 7, at least one hydraulic binder, at least one aggregate, and water.

Description

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Examples

[0237] Part 1—Synthesis of Compounds

[0238] Pyrogallol, gallic acid, formalin and glyoxylic acid were obtained from SIGMA ALDRICH.

[0239] Jeffamine® M2070, M1000 and ED 600 were obtained from HUNTSMAN. The HPLC chain: [0240] Thermo Scientific, UHPLC Ultimate 3000, equipped with a Chromoleon 7.2 software [0241] Column: Thermo Scientific, Acclaim carbonyl C18, Size: 4.6×150 mm, diameter: 120 Å; 5 μm [0242] Detectors: DEDL: SEDEX LC LT ELCD; UV: UHPLC Ultimate 3000.

Example 1: Summary of a Representative Structure 1

[0243] ##STR00012##

[0244] In a three-neck flask with a coolant, 37% formalin (1 equivalent; 0.03 mol; 2.4 g) was added drop by drop to a Jeffamine® M2070 solution (1 equivalent; 0.03 mol; 62.1 g) in 60 ml of water. The reaction medium was stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) was added to the reaction medium and the temperature is increased to 60° C. until pyrogallol disappeared (monitored by HPLC).

Example 2: Summary of a Representative Structure 2

[0245] ##STR00013##

[0246] In a three-neck flask with a coolant, 37% formalin (2 equivalents; 0.06 mol; 4.8 g) was added drop by drop to a Jeffamine® M1000 solution (2 equivalents; 0.06 mol; 62.1 g) in 100 ml of water. The reaction medium was stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) was added to the reaction medium and the temperature was increased to 60° C. until pyrogallol disappeared (monitored by HPLC).

Example 3: Summary of a Representative Structure 3

[0247] ##STR00014##

[0248] In a three-neck flask with a coolant, 50% glyoxylic acid solution (1 equivalent; 0.03 mol; 4.42 g) was added drop by drop to a Jeffamine® M2070 solution (1 equivalent; 0.03 mol; 62.1 g) in 60 ml of water. The reaction medium was stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) was added to the reaction medium and the temperature was increased to 60° C. until pyrogallol disappeared (monitored by HPLC).

Example 4: Summary of a Representative Structure 4

[0249] ##STR00015##

[0250] In a four-neck flask with a Dean Stark and a coolant, Jeffamine® M1000 (1.1 equivalents; 0.194 mol; 193.98 g) and gallic acid (1 equivalent; 0.176 mol; 30 g) were introduced. The reaction medium was increased to 160° C. under vacuum and stirred until pyrogallol disappeared (monitored by HPLC).

Example 5: Summary of a Representative Structure 5

[0251] ##STR00016##

[0252] In a four-neck flask with a Dean Stark and a coolant, Jeffamine® ED-600 (1.1 equivalents; 0.194 mol; 116.39 g) and gallic acid (1 equivalent; 0.176 mol; 30 g) were introduced. The reaction medium was increased to 160° C. under vacuum and stirred until pyrogallol disappeared (monitored by HPLC).

[0253] Part 2—Applications

[0254] AFNOR standardized sand was introduced into the bowl of a PERRIER mixer. After mixing the sand for 30 s at 140 rpm, the pre-wetting water was introduced into the bowl within 15 s. The volume of this water represented one third of the total volume of effective water to be added. Mixing was continued for 15 s and the pre-wetting sand was left to rest for 4 min 30. The cement and lime filler (origin: ERBRAY) were then added to the pre-wetted sand and the whole was mixed at 140 rpm for 1 min before the rest of the total effective water and the whole admixture was introduced over 30 s. The mixer was stopped for the edges of the bowl to be scraped in order to produce homogeneous mortar and the mixing was then resumed for 1 min at 280 rpm.

[0255] Initial water reduction and workability maintenance were obtained by measuring the diameter of the spreading obtained as per the following procedure: [0256] A mold reproducing the Abrahams cone on a one-half scale was filled with the mortar. In order to obtain the spreading, this cone was lifted at 90° from the plate by performing a quarter turn. The spreading was measured with a ruler at 5, 30, 60 and 90 minutes on two diameters at 90° from each other. The indicated measurement was then the average of the two spreadings with an uncertainty of ±10 mm.

[0257] The tests were performed at 20° C.

[0258] The admixture proportioning was determined so as to have an initial spreading between 290 and 310 mm. This proportioning is expressed by weight with respect to the total weight of the binder (cement+filler).

[0259] The chemical compositions used in the application design studies are described below.

TABLE-US-00001 TABLE 1 Chemical composition of the compositions Component Composition 1 Composition 3 Example 1 .sup. 30% Example 3 .sup. 30% Anti-foam  0.3%  0.3% Water 69.7% 69.7%

Example 6: Comparison with a Reference without Admixture

[0260]

TABLE-US-00002 TABLE 2 Hydraulic composition Component Mass (g) EMC I 52.5N Le Teil 555.1 Erbray filler 237.9 AFNOR sand 1,350 Admixture to be adjusted Effective water 277.5

[0261] The results are grouped in Table 3 below, showing the spreading in mm as a function of time in minutes.

TABLE-US-00003 Without admixture Composition 1 Composition 3 Calculated E.S (%) 30.0% 30.3% 30.3% Actual E.S. (%) 29.54% 30.23% 30.15% Proportioning 1.25% 0.80% (% total binder) Alkaline sulfate 0.11% 0.11% 0.11% solution concentration Effective water (g) 277.5 277.5 277.5 Added water (g) 277.5 270.6 273.1 SPREADING (mm) T5 150 300 290 T30 Not measured 190 180 T60 Not measured 170 155 T90 Not measured 150 Not measured

[0262] As observed, the compounds according to the invention have fluidizing capacity. Indeed, at an equal volume of added water, the initial spreading was double when using the two structures in examples 1 and 3.

Example 7: Comparison with a CHRYSO®Fluid Optima 100 Reference

[0263]

TABLE-US-00004 TABLE 4 Hydraulic composition Component Mass (g) EMC I 52.5N Le Teil 615 Erbray filler 265 AFNOR sand 1,350 Admixture to be adjusted Effective water 303

[0264] The results are grouped in Table 5 below, showing the spreading in mm as a function of time in minutes.

TABLE-US-00005 CHRYSO ®Fluid Composition Composition Optima 100 1 3 Calculated E.S (%) 30.0% 30.3% 30.3% Actual E.S. (%) 29.54% 30.23% 30.15% Proportioning 1.25% 1.20% 0.80% (% total binder) Alkaline sulfate 0.11% 0.11% 0.11% solution concentration Effective water (g) 303 303 303 Added water (g) 286.3 295.6 SPREADING (mm) T5 300 295 310 T30 370 210 210 T60 380 180 190 T90 400 160 170 T120 405 Not measured 150

[0265] As observed, the compounds of the invention have a greater fluidizing capacity than that of CHRYSO®Fluid Optima 100. Indeed, at the same volume of added water, the use of active materials for achieving the same initial spreading was lower than the Optima 100.

Example 8: Co-Admixturing with CHRYSO®Fluid Optima 100

[0266]

TABLE-US-00006 TABLE 6 Hydraulic composition Component Mass (g) EMC I 52.5N Le Teil 555.1 Erbray filler 237.9 AFNOR sand 1,350 Admixture to be adjusted Effective water 277.5

[0267] The results are grouped in Table 7 below, showing the spreading in mm as a function of time in minutes.

TABLE-US-00007 CHRYSO ®Fluid CHRYSO ®Fluid Optima 100 + Optima 100 Composition 1 Proportioning 0.70% 0.3% CHRYSO ®Fluid (% total binder) Optima 100 + 0.3% composition 1 Calculated E.S (%) 30.0% 30.0% Actual E.S. (%) 29.54% 29.54% Alkaline sulfate 0.11% 0.11% solution concentration Effective water (g) 277.5 277.5 Added water (g) 273.6 273.6 SPREADING (mm) T5 310 290 T30 315 210 T60 315 240 T90 320 250 T120 340 250 T150 340 250 T180 360 Not measured

[0268] As observed, the use of a compound according to the invention (example 1) in combination with CHRYSO®Fluid Optima 100, leads to obtaining a superior fluidizing capacity while maintaining an interesting workability. In fact, at equal volume of water added, the target spreading was achieved with less active material used for the mixture than for CHRYSO®Fluid Optima 100 alone.

[0269] Table 8 below shows the results for the mechanical properties. The measurements of mechanical resistances to bending and compression were performed as per the standard NF EN 196-1.

TABLE-US-00008 Résistances CHRYSO ®Fluid mécaniques CHRYSO ®Fluid Optima 100 + (Mpa) Optima 100 Composition 1 Rf 24 h 3.3 5.1 Rc 24 h 13.3 23.9 Résistance mécaniques = Mechanical Resistances

[0270] A strong increase in resistance to bending (RF) and compression (RC) was observed after 24 h, which is a performance sought in the field of application.

Example 9: Study on the Robustness with Regard to Alkali

[0271]

TABLE-US-00009 TABLE 9 Hydraulic composition Component Mass (g) EMC I 52.5N Le Teil 555.1 Erbray filler 237.9 AFNOR sand 1,350 Admixture to be adjusted Effective water 277.5

TABLE-US-00010 CHRYSO ®Fluid CHRYSO ®Fluid Composition Composition Optima 100 Optima 100 1 1 Calculated E.S (%) 30.0% 30.0% 30.0% 30.0% Actual E.S. (%) 29.54% 29.54% 30.23% 30.23% Proportioning 0.70% 1.05% 1.25% 1.25% (% total binder) Alkaline sulfate 0.11% 0.60% 0.11% 0.60% ratio in solution Effective water (g) 277.5 277.5 277.5 277.5 Added water (g) 273.6 271.6 270.6 270.6 SPREADING (mm) T5 310 300 300 320 T30 315 270 190 270 T60 315 270 170 240 T90 320 280 150 210 T120 340 285 — 180 T150 340 300 155

[0272] As observed, the use of a compound according to the present invention, leads to obtaining a robustness of the fluidizing capacity with regard to the concentration of alkaline sulfates in solution, unlike with the reference CHRYSO®Fluid Optima 100. In fact, for the same volume of added water, the CHRYSO®Fluid Optima 100 proportioning was increased by 50% in order to obtain the same initial spreading when the soluble alkali concentration increases, while remaining the same for the compound of the invention.

TABLE-US-00011 Mechanical resistances CHRYSO ® Fluid CHRYSO ® Fluid Composition Composition (MPa) Optima 100 Optima 100 1 1 Rf 24 h 3.3 3.8 4.7 5.2 Rc 24 h 13.3 14.5 24.4 30.7

[0273] A strong increase in the resistance to bending and compression is found after 24 h, which is a performance sought in the field of application.

Example 10: Comparative Example with Regard to the Compounds from WO 2009/112647

[0274] The compound with the formula shown below was prepared:

##STR00017##

[0275] In a three-neck flask with a coolant, MPEG 500 (1.1 equivalent, 0.13 mol, 60.0 g), gallic acid (1 equivalent, 0.12 mol, 21.2 g) and paratoluene sulfonic acid (3.0 g) were added and heated to 130° C. under vacuum until the gallic acid disappeared (monitored by HPLC).

[0276] Stability Study at pH=13

[0277] In order to compare the stability of this molecule in the alkaline concrete medium, the compounds in example 1 and in the comparative example 10 were put into solution at pH=13 and their degradation was monitored by HPLC.

[0278] According to the chromatograms obtained, there was no change in the peak corresponding to the compound in example 1 under the study conditions, whereas there was a sharp decrease of the peak corresponding to the compound in example 10 (comparative). Since these peaks are representative of the molecule concentration in the medium, the instability of the structure according to WO 2009/112647 was demonstrated in comparison with the structures according to the invention.