Fluidizing compounds for hydraulic assemblies

Description

[0001] The present invention relates to new fluidizing compounds, intended in particular for use in hydraulic compositions.

[0002] Hydraulic compositions are compositions containing a hydraulic binder. A hydraulic binder is a binder that forms and hardens through a chemical reaction with water. Examples of hydraulic binders include compositions of calcium sulfates and / or aluminates, lime, and cement. Mortars and concretes, particularly precast and ready-mix concretes, are of particular importance. These materials can be used in various applications, including building construction, civil engineering works, and the manufacture of concrete components.

[0003] It is known to add fluidizers (also called plasticizers or superplasticizers) to hydraulic binders to thin the hydraulic composition and thus reduce the water content of the hydraulic binder paste. As a result, the hydraulic binder paste has a denser structure after hardening, leading to higher mechanical strength.

[0004] We know in particular polyoxyalkylene polycarboxylates (PCP), which are particularly effective for fluidizing hydraulic compositions and are also called superplasticizers.

[0005] Other polymer superplasticizers for the fluidization of concrete mortars have been developed, such as the poly(ethylene oxide) bisphosphonate monochains described in application FR 2 696 736, and marketed by the CHRYSO Company under the name CHRYSO ®< Fluid Optima 100. Application FR 2 925 484 of the LAFARGE SA company also describes a type of polymer superplasticizers for the fluidization of concrete mortars consisting of gallic acid ester derivatives.

[0006] However, these superplasticizers exhibit limited water-reducing properties and robustness to clays and alkali sulfates in solution. Furthermore, it should be noted that the chemical stability of concrete in a highly alkaline environment is very limited in the case of the structures described in application FR 2 925 484.

[0007] Therefore, there is currently a need for more efficient fluidizing compounds.

[0008] The present invention therefore aims to provide new compounds that are particularly effective as fluidizers in hydraulic compositions.

[0009] Thus, the present invention relates to a compound of the following formula (I): in which: M is chosen from the group consisting of H, alkali and alkaline earth metals and the +< HNRR' groups, R and R' being chosen independently of each other from H, the (C1-C3)alkyls, linear or branched, and the C1-C3 alcohols, linear or branched; R1 is chosen from the group consisting of H, A1 and the (C1-C4)alkyl groups, linear or branched, when A corresponds to formula (1) below, or, when A corresponds to formula (2) or (3) below, R1 is chosen from the group consisting of H and the (C1-C4)alkyl groups, linear or branched; R2 is chosen from the group consisting of H, OM, M being as defined above and the (C1-C4)alkyl groups, linear or branched; A represents: * a group A 1 with the following formula (1): in which: n is an integer from 1 to 40, preferably from 1 to 31; m is an integer from 1 to 40, preferably from 1 to 31; and Z is chosen from the group consisting of: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH, and (C1-C6)alkyl groups, linear or branched; . -C(=O)-NH- groups; and . -C(R5)=N- groups, R5 being H or Me, preferably H; * a group A2 of the following formula (2): in which: - n is an integer from 1 to 40, preferably from 1 to 31; - m is an integer from 1 to 40, preferably from 1 to 31; - r is 0 or an integer from 1 to 6; and - M, R1 and R2 are as defined above in formula (I); * a group A3 of the following formula (3): in which: n is an integer from 1 to 50, preferably from 1 to 39; the sum 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 1 and R 2 are such as defined above in formula (I); Z is such as defined above in formula (1).

[0010] In the context of the present invention, the following definitions apply: Ct-Cz, where t and z can take values ​​from 1 to 6, a carbon chain being able to have from t to z carbon atoms, for example C1-C4, a carbon chain that can have from 1 to 4 carbon atoms; an alkyl group: a saturated, linear or branched, aliphatic hydrocarbon group comprising, unless otherwise specified, from 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, and pentyl groups.

[0011] Examples of alkali metals include sodium, lithium, and potassium. Examples of alkaline earth metals include magnesium and calcium.

[0012] In the context of the present invention, a C1-C3 alcohol, linear or branched, means a C1-C3 alkyl, linear or branched, substituted by at least one hydroxyl group.

[0013] Preferably, in the above-mentioned formulas (1) and (2), n is an integer from 1 to 31 and m is an integer from 1 to 31.

[0014] According to one embodiment, the compounds of the invention are compounds of the aforementioned formula (I) in which A represents a group A 1 of formula (1) and R 1 is chosen from the group consisting of H, A 1 and (C 1 -C 4 )alkyl groups, linear or branched.

[0015] According to one embodiment, the compounds of the invention conform to the following formula (II): in which: R1 is chosen from the group consisting of H and (C1-C4)alkyl groups, or represents a group A1 of formula (1) as defined above; and M and R2 are as defined above in formula (I) and n and m are as defined above in formula (1).

[0016] Preferably, in formula (II), n is an integer from 1 to 31 and m is an integer from 1 to 31.

[0017] According to one embodiment, in formula (II), R 2 is a group OM, M being such as defined above.

[0018] According to one embodiment, in formula (II), n varies from 19 to 31.

[0019] According to one embodiment, in formula (II), m varies from 3 to 10.

[0020] According to one embodiment, in formula (II), Z is chosen from the group formed: -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched; and -C(=O)-NH- groups.

[0021] According to one embodiment, in formula (II), Z is chosen from the group consisting of the -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched.

[0022] According to one embodiment, in formula (II), Z is a -CHR 3 -NH- group where R 3 is H or COOH, or a -C(=O)-NH- group.

[0023] According to one embodiment, in formula (II), Z is a -CHR 3 -NH- group where R 3 is H or COOH.

[0024] According to one embodiment, the compounds of the invention conform to formula (II), in which: R2 is an OM group, M being as defined above; n varies from 19 to 31; m varies from 3 to 10; and Z is chosen from the group consisting of: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched; and . -C(=O)-NH- groups.

[0025] According to one embodiment, the compounds of the invention conform to formula (II), in which: R 2 is an OM group, M being as defined above; n varies from 19 to 31; m varies from 3 to 10; and Z is chosen from the group consisting of -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched.

[0026] Preferably, the compounds of the invention correspond to formula (II) as defined above, in which R 1 is H or represents a group A 1 of formula (1) as defined above.

[0027] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R1 is H or represents an A1 group of formula (1) as defined above; R2 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: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched; and . -C(=O)-NH- groups.

[0028] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R1 is H or represents an A1 group of formula (1) as defined above; R2 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 -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched.

[0029] According to one embodiment, in formula (II), n is equal to 19.

[0030] According to one embodiment, in formula (II), n is equal to 31.

[0031] According to one embodiment, in formula (II), m is equal to 3.

[0032] According to one embodiment, in formula (II), m is equal to 10.

[0033] A specific group of compounds according to the invention is formed of compounds of formula (II) as defined above, in which n=19 and m=3.

[0034] Another specific group of compounds according to the invention is formed of compounds of formula (II) as defined above, in which n=31 and m=10.

[0035] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R1 is H or represents an A1 group of formula (1) as defined above; R2 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: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched; and . -C(=O)-NH- groups.

[0036] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R1 is H or represents an A1 group of formula (1) as defined above; R2 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 -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched.

[0037] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R1 is H or represents a group A1 of formula (1) as defined above; R2 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: . -CHR3-NH- groups, R3 being chosen from the group consisting of H and COOH; and . -C(=O)-NH- groups.

[0038] Preferably, in this family, n = 19 and m = 3 or n = 31 and m = 10.

[0039] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (II), in which: R 1 is H or represents a group A 1 of formula (1) as defined above; R 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 the groups -CHR 3 -NH-, R 3 being chosen from the group consisting of H and COOH.

[0040] Preferably, in this family, n = 19 and m = 3 or n = 31 and m = 10.

[0041] Among the compounds of formula (II) according to the present invention, particular mention may be made of compounds corresponding to one of the following formulas: m and n being such as defined above, and preferably n = 19 and m = 3 or n = 31 and m = 10.

[0042] Among the compounds of formula (II) according to the present invention, particular mention may be made of compounds corresponding to one of the following formulas: m and n being such as defined above, and preferably n = 19 and m = 3 or n = 31 and m = 10.

[0043] According to one embodiment, the compounds of the invention are compounds of the aforementioned formula (I) in which A represents a group A 2 of formula (2) and R 1 is chosen from the group consisting of H and (C 1 -C 4 )alkyl groups, linear or branched.

[0044] According to one embodiment, the compounds of the invention conform to the following formula (III): in which: R1 is chosen from the group consisting of H and (C1-C4)alkyl groups; and M and R2 are as defined above for formula (I), and n, m and r are as defined above for formula (2).

[0045] Preferably, in formula (III), n is an integer from 1 to 31 and m is an integer from 1 to 31.

[0046] According to one embodiment, in formula (III), R 2 is a group OM, M being such as defined above.

[0047] Preferably, in formula (III), r is 0 or varies from 1 to 3.

[0048] According to one embodiment, in formula (III), R 2 is a group OM, M being such as defined above, and r is 0 or varies from 1 to 3.

[0049] According to one embodiment, in formula (III), R 1 is H.

[0050] A preferred group of compounds according to the invention consists of compounds of formula (III) as defined above, in which R1 is H and R2 is an OM group and r is 0 or varies from 1 to 3, M being as defined above.

[0051] According to one embodiment, in formula (III), n is equal to 19.

[0052] According to one embodiment, in formula (III), n is equal to 31.

[0053] According to one embodiment, in formula (III), m is equal to 3.

[0054] According to one embodiment, in formula (III), m is equal to 10.

[0055] According to one embodiment, in formula (III), r is equal to 3.

[0056] A specific group of compounds according to the invention is formed of compounds of formula (III) as defined above, in which n=19 and m=3.

[0057] Another specific group of compounds according to the invention is formed of compounds of formula (III) as defined above, in which n=31 and m=10.

[0058] According to one embodiment, the compounds of the invention are compounds of the aforementioned formula (I) in which A represents a group A 3 of formula (3) and R 1 is chosen from the group consisting of H and (C 1 -C 4 )alkyl groups, linear or branched.

[0059] According to one embodiment, the compounds of the invention conform to the following formula (IV): in which: R1 is chosen from the group consisting of H and (C1-C4)alkyl groups; and M and R2, n', m' and p' are such as defined above for formula (I), and n', m' and p' are such as defined above for formula (3).

[0060] Preferably, in formula (IV), n is an integer from 1 to 39.

[0061] According to one embodiment, in formula (IV), R 2 is a group OM, M being such as defined above.

[0062] According to one embodiment, in formula (IV), R 2 is a group OM, M being such as defined above, and r is 0 or varies from 1 to 3.

[0063] According to one embodiment, in formula (IV), Z is chosen from the group constituted: . of the -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched; and . of the -C(=O)-NH- groups.

[0064] According to one embodiment, in formula (IV), Z is chosen from the group consisting of the -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched.

[0065] According to one embodiment, in formula (IV), Z is chosen from the group constituted: . of the -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H and COOH; and . of the -C(=O)-NH- groups.

[0066] According to one embodiment, in formula (IV), Z is chosen from the group consisting of the -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H and COOH.

[0067] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R2 is an OM group; and Z is chosen from the group consisting of: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched; and . -C(=O)-NH- groups.

[0068] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R 2 is an OM group; and Z is chosen from the group consisting of -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (C 1 -C 6 )alkyl groups, linear or branched.

[0069] Preferably, in the aforementioned formula (IV), R 1 is H.

[0070] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R1 is H; R2 is an OM group; and Z is chosen from the group consisting of: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched; and . -C(=O)-NH- groups.

[0071] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R1 is H; R2 is an OM group; and Z is chosen from the group consisting of -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, linear or branched.

[0072] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R1 is H; R2 is an OM group; and Z is chosen from the group consisting of: . -CHR3 -NH- groups, R3 being chosen from the group consisting of H and COOH; and . -C(=O)-NH- groups.

[0073] A preferred family of compounds of the invention consists of compounds corresponding to the aforementioned formula (IV), in which: R1 is H; R2 is an OM group; and Z is chosen from the group consisting of the -CHR3 -NH- groups, R3 being chosen from the group consisting of H and COOH.

[0074] Among the compounds of formula (IV) according to the present invention, particular mention may be made of compounds corresponding to the following formula: n', m' and p' being such as defined above.

[0075] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), as a chelating agent for positively charged ions, in particular selected from the group consisting of alkali ions, alkaline earth ions and transition metal ions, and more particularly as a chelating agent for calcium, magnesium, manganese, iron, nickel or cobalt ions.

[0076] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), as a fluidizing agent for hydraulic compositions.

[0077] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), for the adjuvanting of hydraulic binders.

[0078] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), for the adjuvanting of hydraulic binders, alone or in combination with at least one plasticizer and / or superplasticizer.

[0079] In the context of the present invention, the term "hydraulic binder" means any compound that hydrates in the presence of water and whose hydration yields a solid with specific mechanical properties, in particular a cement such as Portland cement, aluminous cement, pozzolanic cement, or anhydrous or semi-hydrated calcium sulfate. The hydraulic binder may be a cement conforming to standard EN197-1 (2001), and in particular Portland cement, mineral additions, especially slag, or a cement containing mineral additions.

[0080] The term "mineral additions" refers to slags (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.2), steelmaking slags, pozzolanic materials (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.3), fly ash (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.4), calcined shale (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.5), limestone (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.6), and silica fume (as defined in the Cement standard NF EN 197-1(2012) paragraph 5.2.6). 5.2.7) or mixtures thereof. Other additions, not currently recognised by the Cement NF EN 197-1(2012) standard, may also be used.These include metakaolins, such as type A metakaolins conforming to standard NF P 18-513 (August 2012), siliceous additions, such as siliceous additions of Qz mineralogy conforming to standard NF P 18-509 (September 2012), aluminosilicates, in particular inorganic geopolymers.

[0081] The compounds of the invention can be used in the adjuvanting of hydraulic binders in combination with plasticizers and / or superplasticizers in a mixture between 1% and 99%.

[0082] Among these plasticizers and / or superplasticizers, among those well known in the technical field, we can cite for example polyoxyalkylene polycarboxylates (PCP) or poly(ethylene oxide) bis-phosphonate monochains described in patent FR 2 696 736, and marketed by the CHRYSO Company under the name CHRYSO ®< Fluid Optima 100.

[0083] Preferably, the compounds of the invention are used in combination with the aforementioned Optima 100, in a mixture of between 1% and 99% Optima 100, and in particular between 25% and 75%.

[0084] Preferably, the compounds of the invention are used in combination with a PCP in a mixture of between 1 and 99% PCP, and in particular between 25% and 75%.

[0085] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV) to reduce the sensitivity to phyllosilicate clays of a hydraulic composition.

[0086] The presence of phyllosilicate clay in sand, preferably montmorillonites, and even more preferably sodium montmorillonites, can significantly affect the workability of hydraulic binder compositions, particularly concrete compositions. Indeed, the layered structure of clays promotes water absorption and the intercalation of elements contained in hydraulic binder compositions, such as superplasticizers. The quantity of clay is generally determined by the methylene blue test ( NF EN 933-9 standard).

[0087] These phenomena cause an increase in the viscosity of the hydraulic binder paste, and therefore a loss of workability. An overdose of plasticizer is then necessary to compensate for its consumption by the clays and maintain the desired performance. A plasticizer can reduce the sensitivity of a hydraulic composition to phyllosilicate clays when the increase in its dosage to achieve iso-spreading is kept to a minimum, for example, between 0% and 20%, when the phyllosilicate clay content varies.

[0088] The present invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV) to decrease the sensitivity to alkali sulfates in solution of a hydraulic composition.

[0089] Alkaline sulfates in solution compete for the adsorption of plasticizers onto cement grains. The quantification of the alkaline sulfate concentration in solution is performed using the method described in "Techniques and Methods of the Road and Bridge Laboratories, Test Method ME48 - 4p - 1997". The plasticizer dosage is therefore dependent on the alkaline sulfate concentration in solution; the higher this concentration, the higher the plasticizer dosage required to achieve the same target performance. A plasticizer reduces the sensitivity of a hydraulic composition to alkaline sulfates in solution when the increase in its dosage to achieve iso-spreading is as small as possible, for example, between 0% and 20%, when the alkaline sulfate concentration in solution varies, for example, from a low level (less than 0.2% by weight of cement) to a high level (greater than 0.6% by weight of cement).

[0090] The invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), for the preparation of a hydraulic composition comprising: a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), at least one hydraulic binder (for example one hydraulic binder, or two hydraulic binders for binary systems or three hydraulic binders for ternary systems), at least one aggregate, and water.

[0091] Hydraulic compositions can include concrete, mortar, screed or grout.

[0092] Hydraulic compositions are prepared conventionally by mixing the aforementioned components. The invention also relates to a method for preparing a hydraulic composition comprising the mixing step: of a compound as defined above, at least one hydraulic binder, at least one aggregate, and water,

[0093] The components are added in any order.

[0094] The compound according to the invention can be added to the other components of the dry hydraulic composition (generally in powder form) or in solution, preferably in aqueous solution.

[0095] Thus, according to another aspect, the invention relates to a fluidizer (or plasticizer) for hydraulic compositions comprising the compound as defined above in solution in a solvent, particularly an aqueous solution, preferably from 5% to 50% by weight of the compound, particularly from 10% to 30% by weight, and especially in the order of 20% by weight relative to the total weight of the solution. The water in said aqueous solution may, in particular, be pre-wetting water. By "pre-wetting water," we mean a portion of the total water used to moisten the aggregates before mixing, thereby simulating the hygrometric state of the aggregates, which is often damp, in a concrete plant or on the construction site.The aqueous solution comprising the compound may optionally include other additives, for example, an antifoaming agent, an anti-air entrainment additive, a setting accelerator or retarder, a rheology modifier, another fluidizer (plasticizer or superplasticizer), and / or any other additive conventionally used in hydraulic compositions. In a preferred embodiment, the aqueous solution comprising the polymer includes a fluidizer, in particular a superplasticizer, for example, CHRYSO® Fluid Premia 180 or CHRYSO® Fluid Premia 196.

[0096] In the context of the present invention, "cement" means cement according to standard EN 197-1 (2001) and in particular cement of type CEM I, CEM II, CEM III, CEM IV or CEM V according to standard Cement NF EN 197-1 (2012). The cement may include mineral additions.

[0097] The term "aggregates" refers to a collection of mineral grains with an average diameter between 0 and 125 mm. Based on their diameter, aggregates are classified into one of the following six categories: fillers, fine sands, sands, gravels, crushed stone, and ballast (standard XP P 18-545). The most commonly used aggregates are: fillers, which have a diameter of less than 2 mm and for which at least 85% of the aggregates have a diameter of less than 1.25 mm and at least 70% of the aggregates have a diameter of less than 0.063 mm, sands with a diameter between 0 and 4 mm (in the NF EN 13-242 standard, the diameter can go up to 6 mm), gravels with a diameter greater than 6.3 mm, and pebbles with a diameter between 2 and 63 mm.

[0098] Sands are therefore included in the definition of aggregate according to the invention.

[0099] The fillers can be of limestone or dolomitic origin, among other things.

[0100] During the mixing stage, other additives may be added, for example a mineral addition and / or additives, for example an anti-air entrainment additive, an anti-foaming agent, a setting accelerator or retarder, a rheology modifying agent, another fluidifier (plasticizer or superplasticizer), including a superplasticizer, for example CHRYSO ®< Fluid Premia 180 or CHRYSO ®< Fluid Premia 196.

[0101] Generally, 0.1% to 1% by dry weight of the compound according to the invention are used in the hydraulic composition.

[0102] The present invention also relates to a fluidizer for hydraulic composition comprising a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV).

[0103] The present invention also relates to a hydraulic composition, in particular selected from concretes, mortars, screeds and grouts, comprising: a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), at least one hydraulic binder, at least one aggregate, and water.

[0104] The hydraulic composition may also include the aforementioned additives. EXAMPLES PART 1 - SYNTHESIS OF COMPOUNDS

[0105] Pyrogallol, gallic acid, formalin and glyoxylic acid were obtained from SIGMA ALDRICH.

[0106] Jeffamine ®< M2070, M1000 and ED 600 were obtained from HUNTSMAN.

[0107] The HPLC Chain: Thermo Scientific, UHPLC Ultimate 3000, equipped with Chromeleon 7.2 software. Column: Thermo Scientific, Acclaim Carbonyl C18, Dimensions: 4.6 x 150 mm, Diameter: 120 Å; 5 µm Detectors: DEDL: SEDEX LC LT ELCD; UV: UHPLC Ultimate 3000. Example 1 : Synthesis of a representative structure 1 :

[0108] with n = 31 and m = 10

[0109] In a three-necked flask fitted with a condenser, a 37% formalin solution (1 equivalent; 0.03 mol; 2.4 g) is added dropwise to a Jeffamine® M2070 solution (1 equivalent; 0.03 mol; 62.1 g) in 60 mL of water. The reaction mixture is stirred at room temperature for 1 h. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction mixture, and the temperature is raised to 60°C until the pyrogallol is completely consumed (monitored by HPLC). Example 2 Synthesis of a representative structure 2:

[0110] with n = 19 and m = 3

[0111] In a three-necked flask fitted with a condenser, a 37% formalin solution (2 equivalents; 0.06 mol; 4.8 g) is added dropwise to a Jeffamine® M1000 solution (2 equivalents; 0.06 mol; 62.1 g) in 100 mL of water. The reaction mixture is stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction mixture, and the temperature is raised to 60°C until the pyrogallol is completely consumed (monitored by HPLC). Example 3 : Synthesis of a representative structure 3 :

[0112] with n = 19 and m = 3

[0113] In a three-chamber flask fitted with a condenser, a 50% glyoxylic acid solution (1 equivalent; 0.03 mol; 4.42 g) is added dropwise to a Jeffamine® M2070 solution (1 equivalent; 0.03 mol; 62.1 g) in 60 mL of water. The reaction mixture is stirred at room temperature for 1 h. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction mixture, and the temperature is raised to 60°C until the pyrogallol is completely consumed (monitored by HPLC). Example 4 Synthesis of a representative structure 4 :

[0114] with n = 19 and m = 3

[0115] In a four-necked flask fitted with a Dean Stark flask and a condenser, Jeffamine®< M1000 (1.1 equivalents; 0.194 mol; 193.98 g) and gallic acid (1 equivalent; 0.176 mol; 30 g) are introduced. The reaction mixture is heated to 160°C under vacuum and stirred until pyrogallol disappears (monitored by HPLC). Example 5: Synthesis of a representative structure 5:

[0116] with n = 9 and m + p = 3.6

[0117] In a four-necked flask fitted with a Dean Stark flask and a condenser, Jeffamine® ED-600 (1.1 equivalents; 0.194 mol; 116.39 g) and gallic acid (1 equivalent; 0.176 mol; 30 g) are introduced. The reaction mixture is heated to 160°C under vacuum and stirred until pyrogallol disappears (monitored by HPLC). PART 2 - APPLICATIONS

[0118] AFNOR-standardized sand is introduced into the bowl of a PERRIER mixer. After mixing the sand for 30 seconds at 140 rpm, pre-wetting water is added to the bowl over 15 seconds. The volume of this water represents one-third of the total effective water volume to be added. Mixing continues for 15 seconds, and the pre-moistened sand is left to rest for 4 minutes and 30 seconds. Next, cement and limestone filler (source: ERBRAY) are added to the pre-moistened sand, and the mixture is mixed at 140 rpm for 1 minute before the remaining effective water and all of the admixture are added over 30 seconds. The mixer is stopped to scrape the sides of the bowl to ensure a homogeneous mortar, and then mixing is resumed for 1 minute at 280 rpm.

[0119] The initial water reduction and workability are determined by measuring the diameter of the resulting slump according to the following procedure: A mold reproducing Abraham's cone at half scale is filled with mortar. To obtain the slump, this cone is lifted to 90° from the plate by rotating it a quarter turn. The slump is measured at 5, 30, 60, and 90 minutes on two diameters at 90° to each other using a ruler. The measurement given is then the average of the two slumps with an uncertainty of ± 10 mm.

[0120] The tests are done at 20°C.

[0121] The dosage of admixture is determined to achieve an initial spread between 290 and 310 mm. This dosage is expressed by weight relative to the total weight of the binder (cement + filler).

[0122] The chemical compositions used in the application studies are explained below. Table 1: Chemical composition of the compositions Component Composition 1 Composition 3 Example 1 30% Example 3 30% Anti-foam 0,3% 0,3% Water 69,7% 69,7% Example 6 Comparison with a reference without additives

[0123] Table 2: Hydraulic composition Component Mass (g) CEM I 52.5N Le Teil 555,1 Filler Erbray 237,9 AFNOR sand 1 350 Adjuvant to wedge Effective water 277,5

[0124] The results are grouped in Table 3 below concerning the spread in mm as a function of time in minutes. No additives Composition 1 Composition 3 ES theo (%) 30,0% 30,3% 30,3% Real ES (%) 29,54% 30,23% 30,15% dosage (% total binder) 1,25% 0,80% Alkaline sulfate levels in solution 0,11% 0,11% 0,11% Effective water (g) 277,5 277,5 277,5 Added water (g) 277,5 270,6 273,1 SPREAD (mm) T5 150 300 290 T30 Not measured 190 180 T60 Not measured 170 155 T90 Not measured 150 Not measured

[0125] As observed, the compounds according to the invention possess a fluidizing power. Indeed, for the same volume of water added, the initial spreading is doubled with the use of the two structures of examples 1 and 3. Example 7 Comparison with a CHRYSO® Fluid Optima 100 reference

[0126] Table 4: Hydraulic composition Component Mass (g) CEM I 52.5N Le Teil 615 Filler Erbray 265 AFNOR sand 1 350 Adjuvant to wedge Effective water 303

[0127] The results are grouped in Table 5 below concerning the spread in mm as a function of time in minutes. CHRYSO ®< Fluid Optima 100 Composition 1 Composition 3 ES theo (%) 30,0% 30,3% 30,3% Real ES (%) 29,54% 30,23% 30,15% dosage (% total binder) 1,25% 1,20% 0,80% Alkaline sulfate levels in solution 0,11% 0,11% 0,11% Effective water (g) 303 303 303 Added water (g) 286,3 295,6 SPREAD (mm) T5 300 295 310 T30 370 210 210 T60 380 180 190 T90 400 160 170 T120 405 Not measured 150

[0128] As observed, the compounds of the invention possess a superior fluidizing power to that of CHRYSO ®< Fluid Optima 100. Indeed, for the same volume of water added, the commitments of active matter to achieve the same initial spreading are lower than for Optima 100. Example 8 Co-adjuvant with CHRYSO® Fluid Optima 100

[0129] Table 6: Hydraulic composition Component Mass (g) CEM I 52.5N Le Teil 555,1 Filler Erbray 237,9 AFNOR sand 1 350 Adjuvant to wedge Effective water 277,5

[0130] The results are grouped in Table 7 below concerning the spread in mm as a function of time in minutes. CHRYSO ®< Fluid Optima 100 CHRYSO ®< Fluid Optima 100 + Composition 1 dosage (% total binder) 0,70% 0.3% of CHRYSO ®< Fluid Optima 100 + 0.3% of Composition 1 ES theo (%) 30,0% 30,0% Real ES (%) 29,54% 29,54% Alkaline sulfate levels in solution 0,11% 0,11% Effective water (g) 277,5 277,5 Added water (g) 273,6 273,6 SPREAD (mm) T5 310 290 T30 315 210 T60 315 240 T90 320 250 T120 340 250 T150 340 250 T180 360 Not measured

[0131] As observed, the use of a compound according to the invention (example 1) in combination with CHRYSO®< Fluid Optima 100 provides superior flowability while maintaining good workability. Indeed, for the same volume of water added, the target spreadability is achieved with a lower active ingredient requirement for the mixture than with CHRYSO®< Fluid Optima 100 alone.

[0132] Table 8 below summarizes the results of the mechanical properties. The measurements of the mechanical resistances to bending and compression were carried out according to standard NF EN 196-1. Mechanical resistances (MPa) CHRYSO ®< Fluid Optima 100 CHRYSO ®< Fluid Optima 100 + Composition 1 RF 24h 3,3 5,1 RC 24h 13,3 23,9

[0133] A strong increase in flexural (Rf) and compressive (Rc) strength is also observed after 24 hours, which is a desired performance in the field of application. Example 9 : Study of robustness to alkalis

[0134] Table 9: Hydraulic composition Component Mass (g) CEM I 52.5N Le Teil 555,1 Filler Erbray 237,9 AFNOR sand 1 350 Adjuvant to wedge Effective water 277,5 CHRYSO ®< Fluid Optima 100 CHRYSO ®< Fluid Optima 100 Composition 1 Composition 1 ES theo (%) 30,0% 30,0% 30,0% 30,0% Real ES (%) 29,54% 29,54% 30,23% 30,23% dosage (% total binder) 0,70% 1,05% 1,25% 1,25% Alkaline sulfate levels in solution 0,11% 0,60% 0,11% 0,60% Effective water (g) 277,5 277,5 277,5 277,5 Added water (g) 273,6 271,6 270,6 270,6 SPREAD (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

[0135] As observed, the use of a compound according to the invention makes it possible to obtain robustness to the level of alkali sulfates in solution of the fluidizing power unlike the reference CHRYSO ®< Fluid Optima 100. Indeed, at equal volume of water added, the dosage of CHRYSO ®< Fluid Optima 100 increases by 50% to obtain the same initial spreading when the level of soluble alkali increases whereas it remains identical for the compound of the invention. Mechanical resistances (MPa) CHRYSO ®< Fluid Optima 100 CHRYSO ®< Fluid Optima 100 Composition 1 Composition 1 RF 24h 3,3 3,8 4,7 5,2 RC 24h 13,3 14,5 24,4 30,7

[0136] A significant increase in flexural and compressive strength is also observed after 24 hours, which is a desired performance in the field of application. Example 10: Comparative example with respect to WO compounds 2009 / 112647

[0137] The compound with the formula below was prepared:

[0138] In a three-necked flask equipped with a condenser, MPEG 500 (1.1 equivalent, 0.13 mol, 60.0g), gallic acid (1 equivalent, 0.12 mol, 21.2g) and para-toluene sulfonic acid (3.0g) are added and heated to 130°C under vacuum until the gallic acid disappears (followed by HPLC). Stability study at pH = 13

[0139] In order to compare the stability of this molecule in the alkaline environment of concrete, the compounds of example 1 and comparative example 10 were put into solution at pH = 13 and their degradation was monitored by HPLC.

[0140] According to the chromatograms obtained, there is no change in the peak corresponding to the compound in Example 1 under the study conditions, whereas a significant decrease is observed in 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 application WO 2009 / 112647 is demonstrated by comparison with the structures according to the invention.

Claims

1. A compound with the following formula (I): wherein: • M is chosen from the group consisting of H, alkaline and alkaline earth metals and +HNRR' groups, R and R' being chosen independently from each other from H, (C1-C3)alkyl, either linear or branched, and alcohols in C1-C3, either linear or branched; • R1 is chosen from the group consisting of H, A1 and (C1-C4)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, R1 is chosen from the group consisting of H and (C1-C4)alkyl groups, either linear or branched; • R2 is chosen from the group consisting of H, OM, M being as defined above and from (C1-C4) alkyl groups, either linear or branched; • A stands for: * a group A1 with the following formula (1): wherein: - n is an integer from 1 to 40, preferentially from 1 to 31; - m is an integer from 1 to 40, preferentially from 1 to 31; and - Z is chosen from the group consisting of: . -CHR3-NH- groups, R3 being chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, either linear or branched; . -C(=O)-NH- groups; and . -C(R5)=N- groups, where R5 is H or Me; * a group A2 with the following formula (2): wherein: - n is an integer from 1 to 40, preferentially from 1 to 31; - m is an integer from 1 to 40, preferentially from 1 to 31; - r is 0 or an integer from 1 to 6; and - M, R1 and R2 are as defined above in formula (I); * a group A3 with the following formula (3): wherein: - n' is an integer from 1 to 50, preferentially from 1 to 39; - 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, R1 and R2 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): wherein: - R1 is chosen from the group consisting of H and (C1-C4)alkyl groups, or stands for a group A1 with formula (1) as defined in claim 1; and - M, R2, n, m are as defined in claim 1.

3. The compound with formula (II) according to claim 2, wherein: - R2 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: . -CHR3-NH- groups, where R3 is chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, either linear or branched; and . -C(=O)-NH- groups.

4. The compound with formula (II) according to claim 3, wherein R1 is H or stands for a group A1 with formula (1) as defined in claim 1.

5. The compound according to claim 1, having the following formula (III): wherein: - R1 is chosen from the group consisting of H and (C1-C4)alkyl groups; and - M, R2, n, m and r are as defined in claim 1.

6. The compound with formula (III) according to claim 5, wherein R1 is H and R2 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): wherein: - R1 is chosen from the group consisting of H and (C1-C4)alkyl groups; and - M, R2, n', m' and p' are as defined in claim 1.

8. The compound with formula (IV) according to claim 7, wherein: - R1 is H; - R2 is an OM group; and - Z is chosen from the group consisting of: . -CHR3-NH- groups, where R3 is chosen from the group consisting of H, COOH and (C1-C6)alkyl groups, either linear or branched; and . -C(=O)-NH- groups.

9. Use of a compound according to any one of claims 1 to 8: - as a chelating agent of positively charged ions, - as a fluidizing agent for hydraulic compositions, - as an admixture to hydraulic binders alone or in combination with at least one plasticizer and / or superplasticizer, - to decrease the sensitivity to phyllosilicate clays of a hydraulic composition, or - to decrease the sensitivity to alkaline sulfates in solution of a hydraulic composition.

10. A hydraulic composition comprising: - a compound according to any one of claims 1 to 8, - at least one hydraulic binder, - at least one aggregate, and - water.