Fluidizing compounds for hydraulic compositions

Abstract

The invention relates to compounds of formula (I) and their use, in particular as chelating agents for positively charged ions or as fluidizers for hydraulic compositions. The invention also relates to hydraulic compositions comprising compounds of formula (I), at least one hydraulic binder, at least one aggregate and water.

Description

Technical Field

[0001] This invention relates to novel fluidizing compounds, and more particularly to novel fluidizing compounds for use in hydraulically setting compositions. Background Art

[0002] Hydraulic compositions are compositions comprising hydraulic binders. Hydraulic binders are binders which are formed and hardened by chemical reaction with water. Compositions of calcium sulfate and / or aluminates, lime and cement can be used as hydraulic binders. Mortars and concretes, especially prefabricated and ready-made concretes, are of particular importance. Such materials can be used in particular for the manufacture of buildings, civil engineering structures or concrete parts.

[0003] It is well known that adding a fluidizing agent (also called a plasticizer or superplasticizer) to a hydraulic binder fluidizes the hydraulic composition, thereby reducing the water content of the hydraulic binder paste. As a result, after hardening, the hydraulic binder paste has a denser structure. This results in a higher mechanical strength.

[0004] Polyoxyethylene polycarboxylates (PCPs) are particularly effective in fluidizing hydraulic compositions and are also known as high-range water reducers.

[0005] Other polymer superplasticizers for concrete mortar fluidization have also been developed, for example, bisphosphate poly(ethylene oxide) monostearate described in patent application FR2696736, which is marketed by CHRYSO as It is sold under the trade name FluidOptima 100. Patent application FR 2 925 484 of LAFARGE SA also discloses a polymer superplasticizer for the fluidization of concrete mortars, which consists of a gallic acid ester derivative.

[0006] However, this type of superplasticizer has limited water reduction and robustness towards clay and alkali metal sulfates in solution. Furthermore, it should be noted that for the structures disclosed in patent application FR2925484, the chemical stability in highly alkaline concrete media is very limited.

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

[0008] It is an object of the present invention to provide novel compounds which are particularly effective as fluidizers in hydraulic compositions. Summary of the invention

[0009] Therefore, the present invention relates to compounds having the following formula (I):

[0010]

[0011] in:

[0012] M is selected from H, alkali metals and alkaline earth metals and + The group consisting of HNRR' groups, R and R' are independently selected from H, (C1-C3) straight or branched alkyl and C1-C3 straight or branched alcohol;

[0013] When A is in accordance with the following formula (1), R1 is selected from the group consisting of H, A1 and (C1-C4) linear or branched alkyl; or, if A is represented by the following formula (2) or (3), R1 is selected from the group consisting of H and (C1-C4) linear or branched alkyl;

[0014] R2 is selected from H, OM and (C1-C4) linear or branched alkyl, wherein M is as defined above;

[0015] A means:

[0016] * A group A1 having the following formula (1):

[0017]

[0018] in:

[0019] - n is an integer between 1 and 40, preferably an integer between 1 and 31;

[0020] - m is an integer between 1 and 40, preferably an integer between 1 and 31; and

[0021] -Z is selected from the group consisting of:

[0022] -CHR3-NH- group, R3 is selected from H, COOH and (C1-C6) straight chain or branched alkyl;

[0023] -C(=O)-NH- group; and

[0024] -C(R5)=N-group, wherein R5 is H or Me, preferably H;

[0025] * A group A2 having the following formula (2):

[0026]

[0027] in:

[0028] - n is an integer between 1 and 40, preferably an integer between 1 and 31;

[0029] - m is an integer between 1 and 40, preferably an integer between 1 and 31;

[0030] -r is 0 or an integer between 1 and 6; and

[0031] -M, R1 and R2 are as defined above in formula (I);

[0032] * A group A3 having the following formula (3):

[0033]

[0034] in:

[0035] - n' is an integer between 1 and 50, preferably an integer between 1 and 39;

[0036] -The sum of m′+p′ varies between 1 and 6;

[0037] - m′ is an integer between 1 and 5;

[0038] - p′ is an integer between 1 and 5; and

[0039] -M, R1 and R2 are as defined above in formula (I);

[0040] -Z is as defined in the above formula (1). DETAILED DESCRIPTION

[0041] Within the framework of the present invention:

[0042] -C t -C z , wherein t and z can take values ​​between 1 and 6, refers to a carbon chain having t to z carbon atoms, for example, C1-C4 refers to a carbon chain having 1 to 4 carbon atoms;

[0043] -Alkyl means, unless otherwise specified, a straight-chain or branched saturated hydrocarbon aliphatic radical comprising 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl or pentyl.

[0044] As the alkali metal, sodium, lithium or potassium may be cited, and as the alkaline earth metal, magnesium and calcium may be cited.

[0045] Within the framework of the present invention, a C1-C3 straight-chain or branched alcohol is understood to mean a straight-chain or branched C1-C3 alkyl group substituted by at least one hydroxyl group.

[0046] Preferably, in the above formulae (1) and (2), n is an integer of 1 to 31, and m is an integer of 1 to 31.

[0047] According to one embodiment, the compound of the present invention is a compound having the above formula (I), wherein A represents a group A1 having formula (1), and R1 is selected from the group consisting of H, A1 and (C1-C4) linear or branched alkyl.

[0048] According to one embodiment, the compound of the present invention has the following formula (II):

[0049]

[0050] in:

[0051] - R1 is selected from the group consisting of H and (C1-C4)alkyl, or represents a group A1 having formula (1) as defined above; and

[0052] - M and R2 are as defined above in formula (I); and

[0053] - n and m are as defined in the above formula (1).

[0054] Preferably, in formula (II), n is an integer from 1 to 31, and m is an integer from 1 to 31.

[0055] According to one embodiment, in formula (II), R2 is an OM group and M is as defined above.

[0056] According to one embodiment, in formula (II), n varies between 19 and 31.

[0057] According to one embodiment, in formula (II), m varies between 3 and 10.

[0058] According to one embodiment, in formula (II), Z is selected from the group consisting of:

[0059] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0060] -C(=O)-NH- group.

[0061] According to one embodiment, in formula (II), Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) linear or branched alkyl.

[0062] According to one embodiment, in formula (II), Z is a CHR3-NH- group, wherein R3 is H or COOH, or a -C(=O)-NH- group.

[0063] According to one embodiment, in formula (II), Z is a -CHR3-NH- group, wherein R3 is H or COOH.

[0064] According to one embodiment, the compounds of the present invention have formula (II), wherein:

[0065] -R2 is an OM group, M is as defined above;

[0066] -n varies between 19 and 31;

[0067] -m varies between 3 and 10; and

[0068] -Z is selected from the group consisting of:

[0069] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0070] -C(=O)-NH- group.

[0071] According to one embodiment, the compounds of the present invention have formula (II), wherein:

[0072] -R2 is an OM group, M is as defined above;

[0073] -n varies between 19 and 31;

[0074] -m varies between 3 and 10; and

[0075] -Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) straight or branched chain alkyl.

[0076] Preferably, the compounds of the invention have the formula (II) as defined above, wherein R1 is H or represents a group A1 having the formula (1) as defined above.

[0077] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0078] - R1 is H or represents a group A1 having the above formula (1);

[0079] -R2 is an OM group;

[0080] -n varies between 19 and 31;

[0081] -m varies between 3 and 10; and

[0082] -Z is selected from the group consisting of:

[0083] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0084] -C(=O)-NH- group.

[0085] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0086] - R1 is H or represents a group A1 having the above formula (1);

[0087] -R2 is an OM group;

[0088] -n varies between 19 and 31;

[0089] -m varies between 3 and 10; and

[0090] -Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) straight or branched chain alkyl.

[0091] According to one embodiment, in formula (II), n is equal to 19.

[0092] According to one embodiment, in formula (II), n is equal to 31.

[0093] According to one embodiment, in formula (II), m is equal to 3.

[0094] According to one embodiment, in formula (II), m is equal to 10.

[0095] A specific group of compounds according to the invention consists of compounds of formula (II) as defined above, wherein n=19 and m=3.

[0096] Another particular group of compounds according to the invention consists of compounds of formula (II) as defined above, wherein n=31 and m=10.

[0097] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0098] - R1 is H or represents a group A1 having the above formula (1);

[0099] -R2 is an OM group;

[0100] -n varies between 19 and 31;

[0101] -m varies between 3 and 10; and

[0102] -Z is selected from the group consisting of:

[0103] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0104] -C(=O)-NH- group.

[0105] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0106] - R1 is H or represents a group A1 having the above formula (1);

[0107] -R2 is an OM group;

[0108] -n varies between 19 and 31;

[0109] -m varies between 3 and 10; and

[0110] -Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) straight or branched chain alkyl.

[0111] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0112] - R1 is H or represents a group A1 having the above formula (1);

[0113] -R2 is an OM group;

[0114] -n varies between 19 and 31;

[0115] -m varies between 3 and 10; and

[0116] -Z is selected from the group consisting of:

[0117] -CHR3-NH- group, R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0118] -C(=O)-NH- group.

[0119] Preferably, in this family, n=19 and m=3, or n=31 and m=10.

[0120] A preferred group of compounds of the present invention consists of compounds having the above formula (II), wherein:

[0121] - R1 is H or represents a group A1 having the above formula (1);

[0122] -R2 is an OM group;

[0123] -n varies between 19 and 31;

[0124] -m varies between 3 and 10; and

[0125] -Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) straight or branched chain alkyl.

[0126] Preferably, in this family, n=19 and m=3, or n=31 and m=10.

[0127] Among the compounds of formula (II) according to the present invention, mention may be made, in particular, of compounds represented by the following formula:

[0128]

[0129]

[0130] m and n are as defined above, preferably n=19 and m=3, or n=31 and m=10.

[0131] Among the compounds of formula (II) according to the present invention, mention may be made, in particular, of compounds represented by the following formula:

[0132]

[0133] m and n are as defined above, preferably n=19 and m=3, or n=31 and m=10.

[0134] According to one embodiment, the compound of the present invention is a compound having the above formula (I), wherein A represents a group A2 having the formula (2), and R1 is selected from H and (C1-C4) linear or branched alkyl.

[0135] According to one embodiment, the compound of the present invention has the following formula (III):

[0136]

[0137] in:

[0138] - R1 is selected from the group consisting of H and (C1-C4) alkyl; and

[0139] - M and R2 are as defined above in formula (I); and

[0140] - n, m and r are as defined in the above formula (2).

[0141] Preferably, in formula (III), n is an integer from 1 to 31, and m is an integer from 1 to 31.

[0142] According to one embodiment, in formula (III), R2 is an OM group and M is as defined above.

[0143] Preferably, in formula (III), r is 0 or varies between 1 and 3.

[0144] According to one embodiment, in formula (III), R2 is an OM group, M is as defined above, and r is 0 or varies between 1 and 3.

[0145] According to one embodiment, in formula (III), R1 is H.

[0146] A preferred group of compounds according to the invention consists of compounds of formula (III) as defined above, wherein R1 is H, R2 is an OM group and r is 0 or varies between 1 and 3 and M is as defined above.

[0147] According to one embodiment, in formula (III), n is equal to 19.

[0148] According to one embodiment, in formula (III), n is equal to 31.

[0149] According to one embodiment, in formula (III), m is equal to 3.

[0150] According to one embodiment, in formula (III), m is equal to 10.

[0151] According to one embodiment, in formula (III), r is equal to 3.

[0152] A specific group of compounds according to the invention consists of compounds of formula (III) as defined above, wherein n=19 and m=3.

[0153] Another specific group of compounds according to the invention consists of compounds of formula (III) as defined above, wherein n=31 and m=10.

[0154] According to one embodiment, the compound of the present invention is a compound having the above formula (I), wherein A represents a group A3 having the formula (3), and R1 is selected from H and (C1-C4) linear or branched alkyl.

[0155] According to one embodiment, the compound of the present invention has the following formula (IV):

[0156]

[0157] in:

[0158] - R1 is selected from the group consisting of H and (C1-C4) alkyl;

[0159] - M and R2, n, m' and p are as defined above for formula (I); and

[0160] - n', m' and p are as defined in the above formula (3).

[0161] Preferably, in formula (IV), n is an integer from 1 to 39.

[0162] According to one embodiment, in formula (IV), R2 is an OM group and M is as defined above.

[0163] According to one embodiment, in formula (IV), R2 is an OM group, M is as defined above, and r is 0 or varies between 1 and 3.

[0164] According to one embodiment, in formula (IV), Z is selected from the group consisting of:

[0165] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0166] -C(=O)-NH- group.

[0167] According to one embodiment, in formula (IV), Z is selected from -CHR3-NH-, and R3 is selected from H, COOH and (C1-C6) linear or branched alkyl.

[0168] According to one embodiment, in formula (IV), Z is selected from the group consisting of:

[0169] -CHR3-NH- group, R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and

[0170] -C(=O)-NH- group.

[0171] According to one embodiment, in formula (IV), Z is selected from -CHR3-NH-, and R3 is selected from H and COOH.

[0172] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0173] - R2 is an OM group; and

[0174] -Z is selected from the group consisting of:

[0175] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight-chain or branched alkyl; and -C(=O)-NH- groups.

[0176] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0177] - R2 is an OM group; and

[0178] -Z is selected from -CHR3-NH-, and R3 is selected from H, COOH and (C1-C6) straight or branched alkyl. Preferably, in the above formula (IV), R1 is H.

[0179] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0180] -R1 is H;

[0181] - R2 is an OM group; and

[0182] -Z is selected from the group consisting of:

[0183] -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight-chain or branched alkyl; and -C(=O)-NH- groups.

[0184] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0185] -R1 is H;

[0186] - R2 is an OM group; and

[0187] -Z is selected from the group -CHR3-NH-, and R3 is selected from the group consisting of H, COOH and (C1-C6) straight or branched chain alkyl.

[0188] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0189] -R1 is H;

[0190] - R2 is an OM group; and

[0191] -Z is selected from the group consisting of:

[0192] -CHR3-NH- group, R3 is selected from H and COOH; and

[0193] -C(=O)-NH- group.

[0194] A preferred group of compounds of the present invention consists of compounds having the above formula (IV), wherein:

[0195] -R1 is H;

[0196] - R2 is an OM group; and

[0197] -Z is selected from the group -CHR3-NH- and R3 is selected from the group consisting of H and COOH.

[0198] Among the compounds of formula (IV) according to the present invention, mention may be made, in particular, of compounds represented by the following formula:

[0199]

[0200] n', m' and p' are as defined above.

[0201] The invention also relates to the use of a compound as defined above, a compound of formula (I) or of one of formulae (II), (III) or (IV) as a chelating agent for positively charged ions, in particular selected from the group consisting of alkali metal ions, alkaline earth metal ions and transition metal ions, more particularly as a chelating agent for calcium, magnesium, manganese, iron, nickel or cobalt ions.

[0202] The invention also relates to the use of a compound as defined above, a compound represented by formula (I) or by one of the formulae (II), (III) or (IV) as a fluidizer for hydraulic compositions.

[0203] The invention also relates to the use of a compound as defined above, a compound represented by formula (I) or one of formulas (II), (III) or (IV) as an admixture for hydraulic binders.

[0204] The invention also relates to a compound as defined above, represented by formula (I) or one of formulas (II), (III) or (IV), used alone or in combination with at least one plasticizer and / or superplasticizer as an admixture for hydraulic binders.

[0205] In the framework of the present invention, the term "hydraulic binder" refers to any compound that has the ability to hydrate in the presence of water, the hydration producing a solid with mechanical properties, including cements such as Portland cement, aluminous cement, pozzolanic cement or anhydrous or hemihydrated calcium sulfate. The hydraulic binder may be a cement in accordance with EN 197-1 (2001), in particular Portland cement, a mineral additive (in particular a slurry) or a cement containing a mineral additive.

[0206] “Mineral additives” means paste (as defined in paragraph 5.2.2 of the cement standard NF EN 197-1 (2012)), steel mill slag, pozzolanic material (as defined in paragraph 5.2.3 of the cement standard NF EN 197-1 (2012)), fly ash (as defined in paragraph 5.2.4 of the cement standard NF EN 197-1 (2012)), calcined schist (as defined in paragraph 5.2.5 of the cement standard NF EN 197-1 (2012)), limestone (as defined in paragraph 5.2.6 of the cement standard NF EN 197-1 (2012)) or silicate fly ash (as defined in subsection 5.2.7 of the cement standard NF EN 197-1 (2012)) or mixtures thereof. Other additives not currently approved by the cement standard NF EN 197-1 (2012) may also be used. In particular, it concerns metakaolins, such as type A metakaolins as defined in standard NF P18-513 (August 2012); siliceous additives, such as silica additives of Qz mineralogical type as defined in standard NF P 18-509 (September 2012); and aluminosilicates, in particular inorganic geopolymer cements.

[0207] The compounds of the invention can be used as admixtures in hydraulic binders in combination with plasticizers and / or superplasticizers in an amount of 1% to 99% in the mixture.

[0208] Among these plasticizers and / or superplasticizers, among the plasticizers and / or superplasticizers well known in the art, the embodiments are polyoxyethylene polycarboxylates (PCP) or poly(ethylene oxide) bisphosphonate monochains described in patent FR2696736, and the polyoxyethylene polycarboxylates (PCP) or poly(ethylene oxide) bisphosphonates monochains described in patent FR2696736, and the polyoxyethylene polycarboxylates (PCP) or polyoxyethylene polycarboxyl ... Those sold under the trade name Fluid Optima 100.

[0209] Preferably, the compounds of the present invention are used in combination with the aforementioned Optima 100, in which the content of Optima is 1% to 99%, especially 25% to 75%.

[0210] Preferably, the compounds of the invention are used in combination with PCP in an amount of 1% to 99%, especially 25% to 75% PCP in the mixture.

[0211] The present invention also relates to the use of a compound represented by the above formula (I) or a compound represented by one of the formulas (II), (III) or (IV) for reducing the sensitivity of a layered silicate clay to a hydraulic composition.

[0212] The presence of phyllosilicate clays, preferably montmorillonite, more preferably sodium montmorillonite, in the sand can strongly influence the workability of hydraulic binder compositions, especially concrete compositions. Indeed, the phyllosilicate clay structure enhances the absorption of water and the embedding of elements contained in the hydraulic binder composition (e.g. superplasticizer). The amount of clay is usually measured by the methylene blue test (NF EN 933-9 standard).

[0213] This phenomenon can lead to an increase in the viscosity of the hydraulic binder slurry, resulting in a loss of workability. It is then necessary to use an over-proportioned fluidizer to compensate for the consumption of clay and maintain the desired properties. When the dosage increase of the hydraulic composition used to achieve uniform spreading is as low as possible (e.g., 0% to 20%), the fluidizer is used to reduce its sensitivity to the phyllosilicate clay of the hydraulic composition as the phyllosilicate clay content of the hydraulic composition changes.

[0214] The present invention also relates to the use of a compound represented by the above formula (I) or a compound represented by one of the formulas (II), (III) or (IV) for reducing the sensitivity of a solution of a hydraulic composition to alkaline sulfate.

[0215] Alkali sulfate in solution is a competitor for the adsorption of fluidizers on cement particles. The content of alkaline sulfate in solution is measured using the method described in "Techniques and methods for road laboratories, test method ME48-4p-1997 (Techniques et méthodes des laboratoires desponts et chaussées, Méthode d'essai ME48-4p-1997)". Therefore, the fluidizer ratio depends on the level of alkaline sulfate in solution: the higher the concentration, the higher the proportion of fluidizer to achieve the same target performance. Fluidizers are used to reduce the sensitivity to alkaline sulfate in solution of hydraulic compositions when the dosage added to achieve uniform spreading is as low as possible (e.g., 0% to 20%), for example, when the level of alkaline sulfate in solution varies, for example, from what is considered to be a low level (less than 0.2% by weight of cement) to a higher level (more than 0.6% by weight of cement).

[0216] The present invention also relates to the use of a compound as defined above (a compound represented by formula (I) or by one of formulas (II), (III) or (IV)) in the preparation of a hydraulic composition comprising:

[0217] - a compound as defined above, a compound represented by formula (I) or a compound represented by one of formulas (II), (III) or (IV);

[0218] - at least one hydraulic binder (for example, one hydraulic binder, or two hydraulic binders for a binary system, or three hydraulic binders for a ternary system);

[0219] - at least one aggregate; and

[0220] -water.

[0221] The hydraulic composition may include concrete, mortar, screed or grout.

[0222] The hydraulic composition is prepared in a conventional manner by mixing the above ingredients. The present invention also relates to a method for preparing a hydraulic composition, the method comprising the steps of mixing the following ingredients:

[0223] - a compound as defined above;

[0224] - at least one hydraulic binder;

[0225] - at least one aggregate; and

[0226] -water,

[0227] The ingredients may be added in any order.

[0228] The compounds according to the invention can be added to the other components of the hydraulic composition either dry (generally in powder form) or in solution, preferably in aqueous solution.

[0229] Therefore, according to another aspect, the present invention relates to a fluidizer (or plasticizer) for a hydraulic composition containing the above-mentioned compound, which is in a solution in a solvent, especially in an aqueous solution, preferably in an amount of 5% to 50% by weight of the compound, especially 10% to 30%, especially about 20% by weight of the total weight of the solution. In particular, the water of the aqueous solution can be pre-wetting water. "Pre-wetting water" refers to a portion of the total water used to wet the aggregate before mixing to simulate the usual wet humidity state of the aggregate in a concrete plant or construction site. The aqueous solution (including the compound) may include other admixtures, for example, a defoamer, an air entraining agent, a setting accelerator or a retarder, a rheology modifier, another fluidizer (plasticizer or superplasticizer) and / or any other admixture commonly used in hydraulic compositions. In a preferred embodiment, the aqueous solution containing a polymer contains a fluidizer, especially a superplasticizer, for example, Fluid Premia 180 or FluidPremia 196 superplasticizer.

[0230] In the framework of the present invention, "cement" means cement conforming to the EN 197-1 (2001) standard, in particular cement of type EMC I, EMC IL, EMC III, EMC IV or EMC V conforming to the NFEN 197-1 (2012) standard. The cement may comprise mineral additives.

[0231] "Aggregate" refers to a group of mineral particles with an average diameter of 0 to 125 mm. Depending on their diameter, aggregates are classified into one of the following six categories: filler, superfine sand, sand, gravel sand mixture, gravel and ballast (XP P 18-545). The most commonly used aggregates are as follows:

[0232] - filler with a diameter less than 2 mm and at least 85% of the aggregates less than 1.25 mm in diameter and at least 70% of the aggregates less than 0.063 mm in diameter,

[0233] - sand, with a diameter between 0 and 4 mm (in the NF EN 13-242 standard; up to 6 mm in diameter),

[0234] - gravel-sand mixtures with a diameter greater than 6.3 mm,

[0235] - Gravel, with a particle size ranging from 2 to 63 mm.

[0236] Therefore, sand is included in the definition of aggregate according to the present invention.

[0237] The filler may be derived, inter alia, from limestone or dolomite.

[0238] During the mixing stage, other admixtures may be added, for example, mineral additives and / or admixtures, for example, air entraining admixtures, defoamers, setting accelerators or retarders, rheology modifiers, another fluidizing agent (plasticizer or superplasticizer), including superplasticizers, e.g. Fluid Premia 180 or Fluid Premia 196 superplasticizer.

[0239] Typically, 0.1% to 1% (by dry weight) of the compound of the present invention is used in the hydraulic composition.

[0240] The present invention also relates to a fluidizer for a hydraulic composition, which comprises the above-mentioned compound, a compound represented by formula (I) or a compound represented by one of formulas (II), (III) or (IV).

[0241] The present invention also relates to a hydraulic composition, in particular a hydraulic composition selected from concrete, mortar, mortar layer and grouting, comprising:

[0242] - a compound as defined above, a compound represented by formula (I) or a compound represented by one of formulas (II), (III) or (IV);

[0243] - at least one hydraulic binder;

[0244] - at least one aggregate; and

[0245] -water.

[0246] The hydraulic composition may also contain the above-mentioned admixtures.

[0247] Example

[0248] Part 1 - Synthesis of compounds

[0249] Pyrogallol-1,3-dimethyl ether, gallic acid, formalin and glyoxylic acid were obtained from SIGMA ALDRICH.

[0250] M2070, M1000 and ED600 were obtained from HUNTSMAN.

[0251] HPLC chain:

[0252] - Thermo Scientific, model UHPLC Ultimate 3000, equipped with Chromoleon version 7.2 software;

[0253] -Chromatographic column: Thermo Scientific, model Acclaim carbonyl C18, size: 4.6×150mm, diameter: 5μm;

[0254] -Detector: DEDL: SEDEX LC LT ELCD; UV: Model UHPLC Ultimate 3000.

[0255] Example 1: Overview of Representative Structure 1:

[0256]

[0257] n=31 and m=10

[0258] In a three-necked flask filled with cooling liquid, 37% formalin (1 equivalent; 0.03 mol; 2.4 g) was added dropwise to 60 ml of water. M2070 solution (1 equivalent; 0.03 mol; 62.1 g). The reaction medium is stirred at room temperature for 1 hour. Pyrogallol-1,3-dimethyl ether (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is raised to 60° C. until pyrogallol-1,3-dimethyl ether disappears (monitored by HPLC).

[0259] Example 2: Overview of Representative Structure 2:

[0260]

[0261] n=19 and m=3

[0262] In a three-necked flask equipped with a coolant, 37% formalin (2 equivalents; 0.06 mol; 4.8 g) was added dropwise to 100 ml of water. M1000 solution (2 equivalents; 0.06 mol; 62.1 g). The reaction medium is stirred at room temperature for 1 hour. Pyrogallol-1,3-dimethyl ether (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is raised to 60° C. until pyrogallol-1,3-dimethyl ether disappears (monitored by HPLC).

[0263] Example 3: Overview of Representative Structure 3:

[0264]

[0265] n=19 and m=3

[0266] In a three-necked flask equipped with a coolant, a 50% glyoxylic acid solution (1 equivalent; 0.03 mol; 4.42 g) was added dropwise to 60 ml of water. M2070 solution (1 equivalent; 0.03 mol; 62.1 g). The reaction medium is stirred at room temperature for 1 hour. Pyrogallol-1,3-dimethyl ether (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is raised to 60° C. until pyrogallol-1,3-dimethyl ether disappears (monitored by HPLC).

[0267] Example 4: Overview of Representative Structure 4:

[0268]

[0269] n=19 and m=3

[0270] In a four-necked flask equipped with Dean Stark and coolant, add M1000 (1.1 equivalents; 0.194 mol; 193.98 g) and gallic acid (1 equivalent; 0.176 mol; 30 g).The reaction medium is brought to 160° C. under vacuum and stirred until pyrogallol-1,3-dimethyl ether disappears (monitored by HPLC).

[0271] Example 5: Overview of Representative Structure 5:

[0272]

[0273] n=9 and m+p=3.6

[0274] In a four-necked flask equipped with Dean Stark and coolant, add ED-600 (1.1 equivalents; 0.194 mol; 116.39 g) and gallic acid (1 equivalent; 0.176 mol; 30 g). The reaction medium is increased to 160° C. under vacuum and stirred until pyrogallol-1,3-dimethyl ether disappears (monitored by HPLC).

[0275] Part 2 - Application

[0276] AFNOR standard sand is introduced into the mixing container of the PERRIER mixer. After mixing the sand at 140 rpm for 30 seconds, pre-wetting water is introduced into the container within 15 seconds. The volume of this water represents one third of the total volume of effective water to be added. Mixing is continued for 15 seconds and the pre-wet sand is left to stand for 4 minutes and 30 seconds. Cement and lime fillers (source: ERBRAY) are then added to the pre-wet sand and the whole mixture is mixed for 1 minute at 140 rpm before the remaining total effective water and the entire admixture are added for 30 seconds. The mixer is stopped in order to scrape the edges of the container so that a homogeneous mortar is produced, and mixing is then continued for 1 minute at 280 rpm.

[0277] The initial water reduction and maintenance of workability were obtained by measuring the spreading diameter obtained according to the following procedure:

[0278] A mould replicating the Abrahams cone on half scale was filled with mortar. To obtain the spread, the cone was lifted 90° from the plate by making a quarter turn. The spread within 90° between two diameters was measured with a ruler at 5, 30, 60 and 90 minutes. The measurements shown are then the average of the two spreads with an uncertainty of ± the mean.

[0279] The test was carried out at 20°C.

[0280] The admixture ratio is determined so that the initial spreading thickness is between 290 and 310 mm. The ratio is expressed as a weight ratio relative to the total weight of the binder (cement + filler).

[0281] The chemical compositions used in the applied design studies are described below.

[0282] Table 1: Chemical composition of the compositions

[0283] Components Composition 1 Composition 3 Example 1 30％ Example 3 30％ Defoaming agent 0.3％ 0.3％ water 69.7％ 69.7％

[0284] Example 6: Comparison with a reference example without an admixture

[0285] Table 2: Hydraulic composition

[0286]

[0287] The test results are grouped in Table 3 below, showing the spread in millimeters versus time in minutes.

[0288]

[0289] As can be observed, the compounds according to the invention have fluidizing capabilities. In fact, with the addition of an equal volume of water, the initial spreading is twice as great when using both structures of Examples 1 and 3.

[0290] Example 7: Comparison of Fluid Optima 100 Reference Example

[0291] Table 4: Hydraulic composition

[0292] Components Mass(g) EMC I 52.5N Standard Cement 615 El Bray Filling 265 AFNOR sand 1,350 Admixtures To be adjusted Effective water 303

[0293] The test results are grouped in Table 5 below, showing the spread in millimeters versus time in minutes.

[0294]

[0295] As can be observed, the compounds of the present invention have Greater fluidization capability of Fluid Optima 100. In fact, with the same volume of water added, the active material takes less than Optima 100 to achieve the same initial spread.

[0296] Example 8: Fluid Optima 100 Co-doping

[0297] Table 6: Hydraulic composition

[0298] Components Mass(g) EMC I 52.5N Standard Cement 555.1 El Bray Filling 237.9 AFNOR sand 1,350 Admixtures To be adjusted Effective water 277.5

[0299] The test results are grouped in Table 7 below, showing the spread in mm versus time (minutes).

[0300]

[0301] As observed, the compound according to the invention (Example 1) and Fluid Optima 100 is used in combination to achieve excellent fluidization while maintaining favorable processability. In fact, with the addition of equal amounts of water, Fluid Optima 100 achieves target spreadability using less active material in the blend than when used alone.

[0302] The results of the mechanical properties are shown below in Table 8. The mechanical resistance in bending and compression was measured according to standard NF EN 196-1.

[0303]

[0304] After 24 hours, a significant increase in the resistance to bending (RF) and compression (RC) was observed, which are sought-after properties in this application area.

[0305] Example 9: Alkali robustness study

[0306] Table 9: Hydraulic composition

[0307] Components Mass(g) EMC I 52.5N Standard Cement 555.1 El Bray Filling 237.9 AFNOR sand 1,350 Admixtures To be adjusted Effective water 277.5

[0308]

[0309] As can be seen, the use of the compounds according to the invention results in a robustness of the fluidization capacity in relation to the alkaline sulfate concentration in the solution, which is in agreement with the results of the reference examples. Fluid Optima 100 is different. In fact, keeping the same amount of the compound of the invention, for the same volume of added water, Fluid Optima 100 was formulated 50% more in order to obtain the same initial spreadability at increasing soluble base concentrations.

[0310]

[0311] After 24 hours, the bending and compression resistance has been significantly improved, which is the desired performance in this application area.

[0312] Example 10: Comparative example of compounds derived from WO 2009 / 112647:

[0313] A compound having the formula:

[0314]

[0315] In a three-necked flask with coolant, MPEG 500 (1.1 eq., 0.13 mol, 60.0 g), gallic acid (1 eq., 0.12 mol, 21.2 g) and p-toluenesulfonic acid (3.0 g) were added and heated to 130°C under vacuum until gallic acid disappeared (monitored by HPLC).

[0316] Stability study at pH = 13

[0317] In order to compare the stability of the molecules in alkaline concrete medium, the compounds in Example 1 and Comparative Example 10 were placed in a solution at pH = 13 and their degradation was monitored by HPLC.

[0318] According to the chromatograms obtained, under the conditions investigated, the peak corresponding to the compound of Example 1 did not change, whereas the peak corresponding to the compound of Example 10 dropped sharply (Comparative Example). Since these peaks represent the concentration of molecules in the medium, the instability of the structure according to WO 2009 / 112647 is demonstrated compared to the structure according to the invention.

Claims

1. A compound of formula (I): in: M is H; When A is represented by the following formula (1), R1 is selected from the group consisting of H, A1 and (C1-C4) linear or branched alkyl, or, if A is represented by the following formula (2), R1 is selected from the group consisting of H and (C1-C4) linear or branched alkyl; R2 is selected from the group consisting of H, OM and (C1-C4) linear or branched alkyl, and M is as defined above; A means: * A group A1 having the following formula (1): in: -n is an integer between 1 and 40; -m is an integer between 1 and 40; and -Z is selected from the group consisting of: -CHR3-NH- group, R3 is selected from H, COOH and (C1-C6) straight chain or branched alkyl; -C(=O)-NH- group; and -C(R5)=N-group, wherein R5 is H or Me; * A group A2 having the following formula (2): in: -n is an integer between 1 and 40; -m is an integer between 1 and 40; -r is 0 or an integer between 1 and 6; and -M, R1 and R2 are as defined above in formula (I).

2. The compound according to claim 1, having the following formula (II): in: - R1 is selected from the group consisting of H and (C1-C4)alkyl, or represents a group A1 of formula (1) as defined in claim 1; and - M, R2, n, m are as defined in claim 1.

3. The compound of formula (II) according to claim 2, wherein: -R2 is an OM group; -n varies between 19 and 31; - m varies between 3 and 10; and -Z is selected from the group consisting of: -CHR3-NH- groups, wherein R3 is selected from H, COOH and (C1-C6) straight or branched alkyl; and -C(=O)-NH- group.

4. The compound of formula (II) according to claim 3, wherein R1 is H or represents a group A1 having the formula (1) as defined in claim 1.

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

6. The compound of formula (III) according to claim 5, wherein R1 is H, R2 is an OM group, and r is 0 or varies between 1 and 3.

7. Use of the compound according to claim 1 in the following applications: - as a fluidizer for hydraulic compositions, or - As an admixture to hydraulic binders, alone or in combination with at least one plasticizer and / or superplasticizer.

8. A hydraulic composition comprising: - A compound according to claim 1; - at least one hydraulic binder; - at least one aggregate; and -water.

Images