Composition of admixtures for hydraulic compositions with reduced clinker content

Abstract

Composition of adjuvants for hydraulic compositions with reduced clinker content The present invention relates to an adjuvant composition comprising, in relation to the total dry mass of active materials of the adjuvant composition: from 35% to 60% by mass of at least one water-reducing or high water-reducing adjuvant chosen from polyalkyl polycarboxylates, from 25% to 45% by mass of at least one water-reducing or high water-reducing adjuvant chosen from polyalkyl phosphonates, from 0.01% to 15% by mass of at least one rheological agent, from 0.1% to 15% by mass of a calcium salt, from 0.1% to 3% by mass of at least one antifoaming agent and / or at least one air-entraining agent, and from 0.05% to 1% by mass of biocidal agent(s). Figure for the abridged version: None

Description

Title of the invention: Composition of additives for hydraulic compositions with reduced clinker content

[0001] The present invention relates to an additive composition intended in particular for hydraulic compositions with reduced clinker content.

[0002] Conventional cementitious compositions contain a significant proportion of clinker. However, current environmental concerns are leading formulators to reduce the clinker content of hydraulic binder compositions in order to reduce their carbon footprint.

[0003] One of the obstacles to the development of such compositions is that replacing clinker with mineral additives leads to a significant reduction in the water / binder ratio of these hydraulic compositions in order to promote the development of strength at all ages, particularly in the short term, and to avoid impacting the durability of the structure. This reduction in the water / binder ratio directly results in an increase in the viscosity of the hydraulic composition. The intrinsic properties of the mineral additives can also cause an increase in the viscosity of the hydraulic composition, as the water demand of some mineral additives is higher than that of conventional cements containing high proportions of clinker.

[0004] Most of the adjuvants known to lower the viscosity of a hydraulic composition with a usual clinker content are not efficient enough to reduce the viscosity of a hydraulic composition with a reduced clinker content, or need to be introduced at levels that are too high to be economically viable.

[0005] There is therefore a need for new adjuvant compositions that can effectively reduce the viscosity of hydraulic compositions, in particular those with reduced clinker content.

[0006] To this end, the invention relates to an adjuvant composition comprising, relative to the total dry mass (in active materials) of the adjuvant composition: - from 35% to 60% by mass of at least one water-reducing or high-water-reducing adjuvant chosen from polycarboxylate polyalkoxylated adjuvants, - 25% to 45% by mass of at least one water-reducing or high-strength water-reducing adjuvant chosen from among polyalkoxylated phosphonates, - from 0.01% to 15% by mass of at least one rheological agent, - from 0.1% to 15% by mass of a calcium salt, - from 0.1% to 3% by mass of at least one antifoaming agent and / or at least one air-entraining agent, and - from 0.05% to 1% by mass of biocidal agent(s).

[0007] The inventors have indeed discovered, surprisingly, that the addition of a rheological agent, known in principle to increase the viscosity of hydraulic compositions, actually makes it possible to decrease their viscosity when it is associated with at least one water-reducing or high water-reducing adjuvant chosen from polyalkoxylated polycarboxylates and at least one water-reducing or high water-reducing adjuvant chosen from polyalkoxylated phosphonates. Rheological agent

[0008] The adjuvant composition according to the invention comprises at least one rheological agent.

[0009] The rheological agents of the invention are preferably compounds capable of increasing the yield stress of the paste of a hydraulic composition and / or the viscosity of the paste of a hydraulic composition. These agents are therefore compounds that, in particular, increase the flow rate of a hydraulic composition comprising them.

[0010] It should be noted that the range of rheological agent(s) content in the additive composition of the invention is broad, as it depends on the nature of the rheological agent. For a given hydraulic composition, particularly one already treated with one or more reducing or high-strength water-reducing agents, the dosage of rheological agent(s) can be adjusted on a case-by-case basis depending on the nature of the rheological agent(s). This dosage is ultimately reflected in the rheological agent(s) content of the additive composition.

[0011] Preferably, the rheological agent(s) and the dosages associated with each rheological agent in a hydraulic composition already modified, in particular by one or more reducing agents or high water reducers and any other additives (excluding rheological agents) (referred to as the "admixed hydraulic composition under study" in the remainder of Protocol A), is or are determined by means of a series of spread measurements on a Schmidt ring (cylinder with an internal diameter of 60 mm and a height of 50 mm) of a volume of 141 mL of paste. The idea is to perform this series of measurements on the paste of the hydraulic composition under study to which one or more rheological agents are to be added, this paste containing an increasingly higher proportion of rheological agents, until the appropriate concentration is found. This test is carried out according to the following protocol (protocol A) in a room maintained at a temperature of 20±2°C and a relative humidity of 65+5%:

[0012] - Preparation of an adjuvanted paste, by mixing with a Rayneri agitator equipped with a 350mm shaft-length, disc-type dissolving blade, diameter For a shaft with an 8 mm diameter and a disc diameter of 80 mm, running at 500 rpm for T0+4 minutes, the mixture consists of water, a hydraulic binder composition, one or more reducing agents or high-strength water reducers, and any other additives in the hydraulic composition being studied. The hydraulic binder composition, the water / binder ratio, the reducing agents or high-strength water reducers and any other additives, and the quantity of reducing agents or high-strength water reducers and any other additives are those of the hydraulic composition being studied. This additive paste is named Po; T0 corresponds to the first contact between the water and the hydraulic binder composition.

[0013] - Filling the Schmidt ring with a volume of 141 mL of adjuvanted paste Po;

[0014] - At T0+5min: Measurement of the spread on two perpendicular diameters after having lifted the cone;

[0015] - The initial spreading value of the paste Po corresponds to the reference value without rheological agent (So);

[0016] - Perform the same test on other Sb, S2, ..., Sx pastes with different dosages in rheological agent than the So paste, all other things being equal. The dosage increment can for example be 0.001% of active material of rheological agent relative to the mass of hydraulic binder;

[0017] - Each spread obtained is noted Si, S2,... Sx, x being the last dosage evaluated.

[0018] - The required dosage is obtained when a measured spreading value is within between 50 and 93% of So, preferably between 60 and 90% of So, preferably between 60 and 80% of So, preferably between 60 and 70% of So, or alternatively preferably between 80% and 90%.

[0019] Preferably, the rheological agent is chosen from:

[0020] - polysaccharide gums, for example diutan gums, gums xanthan gum, welan gum, guar gum and guar ethers, including hydroxyethyl guar, hydroxypropyl guar and carboxymethyl guar, gellan gum, starch and starch ethers,

[0021] - celluloses and cellulose ethers, including the alkyl, hydroxyalkyl and carboxyalkyl,

[0022] - high molar mass polycarboxylates, preferably with a molar mass greater than 100,000 g / mol, preferably with a molar mass greater than 200,000 g / mol,

[0023] - polyethylene glycol (PEG) and polyethylene glycol monomethyl ether (MPEG), preferably with a molar mass greater than 100,000 g / mol,

[0024] - latexes, for example those of the methacrylic copolymer and acrylate ester type ethyl,

[0025] - polyacrylamides,

[0026] - polyvinyl alcohols,

[0027] - clays, for example sepiolite and bentonite type clays,

[0028] - sodium alginates, and

[0029] - any one of their mixtures.

[0030] Preferably, the rheological agent is chosen from:

[0031] - polysaccharide gums, for example diutan gums, gums xanthan gum, welan gum, guar gum and guar ethers, including hydroxyethyl guar, hydroxypropyl guar and carboxymethyl guar, gellan gum, starch and starch ethers,

[0032] - celluloses and cellulose ethers, including the alkyl, hydroxyalkyl and carboxyalkyl,

[0033] - high molar mass polycarboxylates, preferably with a molar mass greater than 100,000 g / mol, preferably with a molar mass greater than 200,000 g / mol, and

[0034] - any one of their mixtures.

[0035] Preferably, the latexes comprise (or are made of) at least one polymer and / or copolymer selected from the group consisting of homopolymers of (meth)acrylic acid, and esters of these acids having the ester group in C1 to C12, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, 2-ethylbutyl, 2-heptylhexyl, copolymers of (meth)acrylic acid and / or esters of these acids having the ester group in C1 to C12, vinyl and (meth)acrylic acid copolymers, vinyl and C12 Cl ester copolymers, (meth)acrylic acid copolymers, (meth)acrylic acid and (meth)acrylic ester copolymers, styrene-(meth)acrylic copolymers, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, acrylic / urethane copolymers, styrene-butadiene copolymers.

[0036] Preferably, the total mass content of rheological agent ranges from 0.01% to 12% by mass, preferably from 0.02% to 10% by mass, preferably from 0.03% to 10% by mass, preferably from 0.04% to 10% by mass, relative to the total dry mass (in active materials) of the adjuvant composition.

[0037] If the adjuvant composition includes several (at least two) rheological agents, the above content ranges therefore refer to the total content of all the rheological agents, relative to the total dry mass (in active materials) of the adjuvant composition.

[0038] Water-reducing admixture or high water-reducing agent selected from polycarboxylate polyalkoxylated

[0039]

[0040] The adjuvant composition of the invention comprises at least one water-reducing or high-water-reducing adjuvant selected from polycarboxylate polyalkoxylated polymers. Preferably, polycarboxylate polyalkoxylated polymers comprise units of formulas (I) and (II), and optionally units of formula (III), as follows: R2 (I) R7 m XR1 (H) L

[0041]

[0042]

[0043]

[0044]

[0045] W +■ R11 OR 16 II 0R1° DRW OR.1 Ü in which - “R2” and “R3” each independently represent a hydrogen or a methyl group, - "M" each independently represents H+ or a valence cation v chosen from an alkali metal cation, an alkaline earth metal cation, a divalent or trivalent metal cation, an ammonium cation or an organic ammonium cation, - when "M" represents H+, "v" represents 1, and when "M" represents a cation as defined above, "v" is the valence of the cation M, - “R7” and “R8” each independently represent a hydrogen, a methyl, or a group of formula -CO00(M)i / v with M and v as defined above,

[0046] - "m" represents 0, 1 or 2,

[0047] - "p" represents 0 or 1,

[0048] - "X" is O or NR9, "R9" representing H, a C1-C20 alkyl group, a group cycloalkyl or an alkylaryl group, and

[0049] - "RI" represents a C1-C20 alkyl group, a cycloalkyl group, a group alkylaryl, or -[Alkyl-O]z-R6, in which the "Alkyl" in each [Alkyl-O] unit independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, and "R6" represents H, a Cl- to C2O alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is an integer from 2 to 250,

[0050] - "a" is a number from 0.05 to 0.95, "a" being the mole fraction of units of formula (I) in the polymer,

[0051] - "b" is a number ranging from 0.05 to 0.95, "b" being the mole fraction of units of formula (II) in the polymer,

[0052] - "L" represents a bonding group to the main chain of the polymer, and is in particular chosen from a direct bond (no atom between the main chain and the W group or the carbon bearing the RI 1 group), an oxygen atom, an -NR12- ​​group, R12 being a hydrogen or an alkyl group in Cl to C6, and an alkylene group in C1-C6, preferably L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom,

[0053] - n = 0 or 1, and if n = 1, "W" is a spacer group, in particular a group an alkylene in Cl at C20 preferably in C1-C6, possibly substituted, or a group of formula -[Alkyl-O]t- in which the 'Alkyl' of each [Alkyl-O] unit independently represents an alkylene group comprising 2 to 4 carbon atoms, and 't' is an integer ranging from 1 to 500, preferably W is an alkylene group in Cl at C6,

[0054] - "RIO" each independently represents a monovalent group, in particular chosen from a hydrogen, a C6 Cl alkyl group, and a formula group -[Alkyl-O]t-R13 in the "Alkyl" of each unit [Alkyl-O] each independently represents an alkylene group of 2 to 4 carbon atoms, "t" is an integer ranging from 1 to 500 and "R13" is chosen from a hydrogen and a C3 Cl alkyl, or "RIO" is a cation, notably an alkali, alkaline earth or ammonium cation (and then the last O of the -[Alkyl-O]t group is O);

[0055] - “RI 1” is a monovalent group, in particular is chosen from an atom of hydrogen, a hydroxyl group and an alkyl group in Cl to CIO, preferably "RI 1" is a hydroxyl group; and

[0056] - "c" is a number ranging from 0 to 0.15, "c" being the mole fraction of units of formula (III) in the polymer.

[0057] An atom or group of atoms defined as "representing independently" or "each representing independently" means that each of these atoms or groups of atoms can each be different from one unit of the polymer to another.

[0058] Preferably, polycarboxylate polyalkoxylated polymers have a comb-like structure.

[0059] The following embodiments for formulas (I), (II) and (III) of the polycarboxylate polyalkoxylated polymer units can be considered independently or combined with each other in any combination:

[0060] - "R2" represents H, and / or

[0061] - “R7” represents H, and / or

[0062] - "R3" each independently represents a hydrogen or a methyl, and / or

[0063] - "R8" each independently represents a hydrogen or a methyl, and / or

[0064] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, and / or

[0065] - X = O, and / or

[0066] - RI = -[Alkyl-O]z-R6, preferably with:

[0067] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0068] - at least 80% of the Alkyl in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0069] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 25 to 75, and / or

[0070] - "R6" represents H or Me, and / or

[0071] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation being preferably chosen from an ammonium salt NH4+, a primary, secondary, tertiary or quaternary ammonium cation and an alkali metal cation, such as a sodium, lithium or potassium ion, and the divalent cation being preferably an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0072] - "a" is a number from 0.20 to 0.90, preferably "a" is a number from 0.40 to 0.85, and / or

[0073] - "b" is a number from 0.10 to 0.80, preferably "b" is a number from 0.15 to 0.60, and / or

[0074] - n = 0, and / or

[0075] - L is an oxygen atom, and / or

[0076] - "RIO" is a hydrogen, and / or

[0077] - “RI 1” is a hydroxyl group, and / or

[0078] - "c" is a number from 0 to 0.12, preferably from 0 to 0.10.

[0079] Preferably, in units of formula (I):

[0080] - "R2" represents H,

[0081] - "R3" each independently represents a hydrogen or a methyl,

[0082] - "M" is H, sodium or calcium, preferably H,

[0083] - "a" is a number from 0.20 to 0.90, preferably "a" is a number from from 0.40 to 0.85.

[0084] Preferably, in units of formula (II):

[0085] - “R7” represents H,

[0086] - "R8" each independently represents a hydrogen or a methyl,

[0087] - X = O,

[0088] - RI = -[Alkyl-O]z-R6, preferably with:

[0089] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0090] - at least 80% of the "Alkyl" of the group -[Alkyl-O]z- represent -CH2-CH2-, or even all the "Alkyl" in the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0091] - "z" represents an integer from 5 to 200, in particular from 10 to 100, of preference from 25 to 75, and / or

[0092] - “R6” represents H or Me,

[0093] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, and

[0094] - "b" is a number from 0.10 to 0.80, preferably "b" is a number from from 0.15 to 0.60.

[0095] Preferably, in the units of formula (III) (if present):

[0096] - n = 0,

[0097] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an atom of oxygen,

[0098] - "RIO" each independently represents a hydrogen, an alkyl group in C1-C6, or "RIO", is a cation, in particular an alkali, alkaline earth, or ammonium cation; preferably, RIO is a hydrogen.

[0099] - “RI 1” is a hydroxyl group, and

[0100] - "c" is a number from 0 to 0.12, preferably from 0 to 0.10.

[0101] According to one embodiment, “c” = 0. In other words, the polymer does not comprise formula units (III).

[0102] According to one embodiment (Ml), the formula units (II) of the polycarboxylate polyalkoxylated polymers are such that p = 0 and m = 1 or 2, preferably 1, and "c" = 0.

[0103] Preferably, according to this embodiment (Ml):

[0104] - "R2" represents H, and / or

[0105] - “R7” represents H, and / or

[0106] - "R3" each independently represents a hydrogen or a methyl, of preference R3 = H and / or

[0107] - "R8" each independently represents a hydrogen or a methyl, of preference R8 = Me, and / or

[0108] - X = O, and / or

[0109] - RI = -[Alkyl-O]z-R6, preferably with:

[0110] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0111] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0112] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 25 to 75, and / or

[0113] - "R6" represents H or Me, preferably "R6" represents H, and / or

[0114] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation being preferably chosen from an ammonium salt NH4+, a primary, secondary, tertiary or quaternary ammonium cation and an alkali metal cation, such as a sodium, lithium or potassium ion, and the divalent cation being preferably an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0115] - "a" is a number from 0.30 to 0.95, preferably a is a number from 0.50 to 0.90, and / Or

[0116] - "b" is a number from 0.05 to 0.70, preferably b is a number from 0.10 to 0.50.

[0117] Preferably, according to (Ml):

[0118] - "R2" represents H,

[0119] - "R3" represents each independently H or a methyl, advantageously is H,

[0120] - "M" is H, sodium or calcium, preferably H,

[0121] - "R7" represents H,

[0122] - "R8" represents each independently H or a methyl, advantageously is a methyl,

[0123] - X = O,

[0124] - RI = -[Alkyl-O]z-R6, preferably with:

[0125] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0126] - at least 80% of the "Alkyl" of the group -[Alkyl-O]z- represent -CH2-CH2-, or even all the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, and / or

[0127] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 25 to 75, and / or

[0128] - "R6" represents H or Me, preferably "R6" represents H.

[0129] - "a" is a number from 0.30 to 0.95, preferably "a" is a number from 0.50 to 0.90, and

[0130] - "b" is a number from 0.05 to 0.70, preferably "b" is a number from 0.10 to 0.50.

[0131] According to another embodiment (M2), the formula units (II) of the polycarboxylate polyalkoxylated polymers are such that p = 1 and m = 0.

[0132] Preferably, according to this embodiment (M2):

[0133] - "R2" represents H, and / or

[0134] - "R7" represents H, and / or

[0135] - "R3" each independently represents a hydrogen or a methyl, and / or

[0136] - "R8" each independently represents a hydrogen or a methyl, and / or

[0137] - X = O, and / or

[0138] - RI = -[Alkyl-O]z-R6, preferably with:

[0139] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0140] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0141] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 50, and / or

[0142] - "R6" represents H or Me, preferably R6 represents Me,

[0143] and / or

[0144] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation being preferably chosen from an ammonium salt NH4+, a primary, secondary, tertiary or quaternary ammonium cation and an alkali metal cation, such as a sodium, lithium or potassium ion, and the divalent cation being preferably an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0145] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or

[0146] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0147] - n = 0, and / or

[0148] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an atom of oxygen,

[0149] - "RIO" each independently represents a hydrogen, an alkyl group in C1-C6, or "RIO", is a cation, in particular an alkali, alkaline earth, or ammonium cation; preferably, RIO is a hydrogen.

[0150] - "RI 1" is a hydroxyl group, and

[0151] - "c" is a number from 0 to 0.12, preferably from 0 to 0.10.

[0152] Preferably, according to (M2):

[0153] - "R2" represents H,

[0154] - "R3" represents each independently H or a methyl group,

[0155] - "M" is H, sodium or calcium, preferably H,

[0156] - "R7" represents H,

[0157] - "R8" represents each independently H or a methyl group,

[0158] -X = O,

[0159] - RI = -[Alkyl-O]z-R6, preferably with:

[0160] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0161] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0162] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 50, and / or

[0163] - "R6" represents H or Me, preferably "R6" represents Me.

[0164] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70,

[0165] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60,

[0166] - L is an oxygen atom,

[0167] - "RIO" is a hydrogen,

[0168] - “RI 1” is a hydroxyl group,

[0169] - "c" is a number from 0 to 0.12, preferably from 0 to 0.10.

[0170] According to a particular embodiment (M2-1) of the embodiment in which the formula units (II) of the polycarboxylate polyalkoxylated polymers are such that p = 1 and m = 0, the polymer comprises units (III).

[0171] Thus, "c" is preferably strictly greater than 0. Preferably, "c" is a number from 0.005 to 0.15, preferably from 0.01 to 0.12, preferably from 0.02 to 0.010, preferably from 0.04 to 0.08.

[0172] According to this alternative (M2-1),

[0173] - "R2" represents H, and / or

[0174] - "R7" represents H, and / or

[0175] - "R3" each independently represents a hydrogen or a methyl, of preferably a methyl group, and / or

[0176] - "R8" each independently represents a hydrogen or a methyl, of preferably a methyl group, and / or

[0177] - X = O, and / or

[0178] - RI = -[Alkyl-O]z-R6, preferably with:

[0179] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0180] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0181] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 50, and / or

[0182] - "R6" represents H or Me, preferably R6 represents Me,

[0183] and / or

[0184] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation being preferably chosen from an ammonium salt NH4+, a primary, secondary, tertiary or quaternary ammonium cation and an alkali metal cation, such as a sodium, lithium or potassium ion, and the divalent cation being preferably an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0185] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or

[0186] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0187] - n = 0, and / or

[0188] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an atom of oxygen,

[0189] - "RIO" each independently represents a hydrogen, an alkyl group in C1-C6, or "RIO", is a cation, in particular an alkali, alkaline earth, or ammonium cation; preferably, RIO is a hydrogen.

[0190] - "RI 1" is a hydroxyl group, and

[0191] - "c" is a number ranging from 0.005 to 0.15, preferably from 0.01 to 0.12, of preferably from 0.02 to 0.010, preferably from 0.04 to 0.08.

[0192] According to another embodiment (M3), the formula units (II) are present in the form of two distinct subunits (Ilb') and (Ilb”). The two subunits (Ilb') and (Ilb”) are of formula (II), according to any embodiment of the units of formula (II) defined above, but are different from each other. Units (I), and (III) if present, are according to any embodiment defined above.

[0193] Preferably, according to this embodiment, "a" is a number from 0.30 to 0.80, preferably from 0.40 to 0.70, alternatively from 0.25 to 0.50, "a" being the mole fraction of units of formula (I) in the polymer, "b'" is a number from 0.10 to 0.35, preferably from 0.15 to 0.30, alternatively from 0.10 to 0.25, "b'" being the mole fraction of units (Ilb') in the polymer, and "b"" is a number from 0.10 to 0.35, preferably from 0.15 to 0.30, alternatively from 0.25 to 0.50, "b"" being the mole fraction of units (Ilb") in the polymer.

[0194] Preferably, according to this embodiment, “c” = 0. Preferably, the polymer therefore does not comprise (III) units.

[0195] Preferably, in units (Ilb'):

[0196] - "R7" represents H,

[0197] - "R8" each independently represents a hydrogen or a methyl, of preference R8 = Me,

[0198] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, preferably p = 0 and m = 1,

[0199] - X = O,

[0200] - RI = -[Alkyl-O]z-R6, preferably with:

[0201] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0202] - at least 80% of the Alkyl of the group -[Alkyl-O]z- represent -CH2-CH2-, or even all the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, and / or

[0203] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 50, alternatively from 30 to 60, and / or

[0204] - "R6" represents H or Me, preferably "R6" represents H.

[0205] - "b'" is a number from 0.10 to 0.35, preferably from 0.15 to 0.30, alternatively from 0.10 to 0.25, where "b'" is the mole fraction of formula units (Ilb') in the polymer.

[0206] Preferably, in units (Ilb”):

[0207] - "R7" represents H,

[0208] - "R8" each independently represents a hydrogen or a methyl, of preference R8 = H,

[0209] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, preferably p = 1 and m = 0,

[0210] - X = O,

[0211] - RI = -[Alkyl-O]z-R6, preferably with:

[0212] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0213] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0214] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 30, alternately from 5 to 15, and / or

[0215] - "R6" represents H or Me, preferably "R6" represents Me.

[0216] - "b" is a number from 0.10 to 0.35, preferably from 0.15 to 0.30, alternatively from 0.25 to 0.50, where “b” is the mole fraction of formula units (Ilb”) in the polymer.

[0217] Preferably, the water-reducing or high-water-reducing adjuvant chosen from polyalkyl polycarboxylates is a mixture of at least two, or even at least three, polyalkyl polycarboxylate polymers as defined above.

[0218] More preferably, the water-reducing or high-reducing adjuvant chosen from polycarboxylate polyalkoxylated compounds comprises a mixture:

[0219] - of at least one polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) in which p = 0, m = letc = 0 according to any corresponding embodiment defined above, preferably according to embodiment (Ml) as described above,

[0220] - of at least one polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) and (III) in which p = 1, m = 0 and c is strictly greater than 0, according to any corresponding embodiment defined above, preferably according to embodiment (M2-1) as described above.

[0221] Advantageously, the water-reducing or high-reducing adjuvant selected from polyalkyl polycarboxylates comprises a mixture:

[0222] - of a first polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) in which p = 0, m = 1 and c = 0, preferably according to embodiment (M1) as described above,

[0223] - of a second polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) in which p = 0, m = 1 and c = 0, and different from the first polycarboxylate polyalkoxylated polymer, preferably according to embodiment (Ml) as described above, and

[0224] - of a third polymer polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) and (III) in which p = 1, m = 0 and c is strictly greater than 0, according to any corresponding embodiment defined above, preferably according to embodiment (M2-1) as described above.

[0225] Even more advantageously:

[0226] - the first polycarboxylate polyalkoxylated polymer is such that "a" is a number from 0.30 to 0.70, preferably "a" is a number from 0.50 to 0.70, and "b" is a number from 0.25 to 0.70, preferably "b" is a number from 0.30 to 0.60,

[0227] - the second polycarboxylate polyalkoxylated polymer is such that "a" is a number from 0.70 to 0.95, preferably "a" is a number from 0.75 to 0.90, and "b" is a number from 0.05 to 0.25, preferably "b" is a number from 0.10 to 0.20.

[0228] Preferably, the first and second polycarboxylate polyalkoxylated polymers differ only in the value of "a" and "b".

[0229] Thus, preferably, in the first and second polycarboxylate polyalkoxylated polymers:

[0230] - "R2" represents H,

[0231] - "R3" represents each independently H or a methyl, advantageously is H,

[0232] - "M" is H, sodium or calcium, preferably H,

[0233] - "R7" represents H,

[0234] - "R8" represents each independently H or a methyl, advantageously is a methyl,

[0235] - X = O,

[0236] - RI = -[Alkyl-O]z-R6, preferably with:

[0237] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0238] - at least 80% of the "Alkyl" of the group -[Alkyl-O]z- represent -CH2-CH2-, or even all the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, and / or

[0239] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 25 to 75, and / or

[0240] - "R6" represents H or Me, preferably "R6" represents H.

[0241] Preferably, in the third polymer: polyalkyl polycarboxylate polymer

[0242] - "R2" represents H, and / or

[0243] - "R7" represents H, and / or

[0244] - "R3" each independently represents a hydrogen or a methyl, of preferably a methyl group, and / or

[0245] - "R8" each independently represents a hydrogen or a methyl, of preferably a methyl group, and / or

[0246] - X = O, and / or

[0247] - RI = -[Alkyl-O]z-R6, preferably with:

[0248] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0249] - at least 80% of the Alkyls in the -[Alkyl-O]z- group represent -CH2-CH2-, or even all The alkyls of the group -[Alkyl-O]z- represent -CH2-CH2-, and / or

[0250] - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 15 to 50, and / or

[0251] - "R6" represents H or Me, preferably R6 represents Me,

[0252] and / or

[0253] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation being preferably chosen from an ammonium salt NH4+, a primary, secondary, tertiary or quaternary ammonium cation and an alkali metal cation, such as a sodium, lithium or potassium ion, and the divalent cation being preferably an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0254] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or

[0255] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0256] - n = 0, and / or

[0257] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an atom of oxygen,

[0258] - "RIO" each independently represents a hydrogen, an alkyl group in C1-C6, or "RIO", is a cation, in particular an alkali, alkaline earth, or ammonium cation; preferably, RIO is a hydrogen.

[0259] - "RI 1" is a hydroxyl group, and

[0260] - "c" is a number ranging from 0.005 to 0.15, preferably from 0.01 to 0.12, of preferably from 0.02 to 0.010, preferably from 0.04 to 0.08.

[0261] Alternatively, the second polyalkyloxylated polycarboxylate polymer may be according to embodiment (M3) as described above, wherein the formula units (II) are present in the form of two distinct subunits (Ilb') and (Ilb”). The first and third polyalkyloxylated polycarboxylate polymers remain as defined above.

[0262] Preferably, the total mass content of water-reducing adjuvant or high water reducer selected from polyalkyl polycarboxylates ranges from 40% to 60% by mass, preferably from 44% to 55% by mass, relative to the total dry mass (in active materials) of the adjuvant composition.

[0263] If the adjuvant composition includes several (at least two) water-reducing or high-water-reducing adjuvants selected from polyalkyl polycarboxylates, the above content ranges therefore refer to the total content of all the water-reducing or high-water-reducing adjuvants selected from polyalkyl polycarboxylates, relative to the total dry mass (of active materials) of the adjuvant composition.

[0264] In particular, the mass content of first polycarboxylate polyalkoxylated polymer ranges from 15% to 35% by mass, preferably from 20% to 30% by mass, relative to the total dry mass (in active materials) of the adjuvant composition.

[0265] In particular, the mass content of the second polycarboxylate polyalkoxylated polymer ranges from 5% to 20% by mass, preferably from 8% to 12% by mass, relative to the total dry mass (of active materials) of the adjuvant composition.

[0266] In particular, the mass content of the third polycarboxylate polyalkoxylated polymer ranges from 5% to 20% by mass, preferably from 8% to 20% by mass, relative to the total dry mass (of active materials) of the adjuvant composition.

[0267] Water-reducing admixture or high water-reducing admixture selected from polyalkoxylated phosphonates

[0268] The adjuvant composition of the invention comprises at least one water-reducing or high water-reducing adjuvant selected from polyalkoxylated phosphonates.

[0269] Preferably, the polyalkoxylated phosphonate polymers have the following formula (IV): \ A IX > < H ? W

[0270] in which

[0271] - "R5" is a hydrogen atom or a monovalent hydrocarbon group comprising from 1 to 18 carbon atoms and possibly one or more heteroatoms;

[0272] - the "Ri"s are similar or different from each other and represent an alkylene such as ethylene, propylene, butylene, amylene, octylene or cyclohexene, or an arylene such as styrene or methylstyrene, the "Ri" possibly containing one or more heteroatoms;

[0273] - “Q” is a hydrocarbon group comprising from 2 to 18 carbon atoms and possibly one or more heteroatoms;

[0274] - "A" is an alkylene group comprising 1 to 5 carbon atoms;

[0275] - the "Rj"s are similar or different from each other and can be chosen from:

[0276] - the group A-PO3H2, A having the aforementioned meaning,

[0277] - an alkyl group comprising from 1 to 18 carbon atoms and capable of bearing groupings [R5-O(Ri-O)m], R5 and Ri having the aforementioned meanings,

[0278] - "m" is a number greater than or equal to 0,

[0279] - "r" is the number of [R5-O(Ri-O)m] groups carried by the set of Rj,

[0280] - "q" is the number of [R5-O(Ri-O)m] groups carried by Q, the sum

[0281] - "r+q" is between 1 and 10,

[0282] - "y" is an integer between 1 and 3,

[0283] - "Q", "N" and the "Rj" can together form one or more cycles, this or these cycles which may also contain one or more other heteroatoms.

[0284] In a particularly preferred manner, polyalkoxylated phosphonates consist of a water-soluble or water-dispersible organic compound comprising at least one amino-di-(alkylene-phosphonic) group and at least one polyoxyalkylated chain or at least one of its salts.

[0285] Preferably, the polyalkoxylated phosphonate is a compound of formula (IV) in which:

[0286] “R5” is a hydrogen atom or a monovalent, saturated hydrocarbon group or not, comprising from 1 to 8 carbon atoms and possibly one or more heteroatoms;

[0287] the "Ri" represent ethylene or propylene or a mixture of ethylene or propylene, preferably 60% to 100% of the "Ri" are ethylene groups;

[0288] “Q” is a hydrocarbon group comprising 2 to 8 carbon atoms and, possibly, one or more heteroatoms;

[0289] “A” is the methylene group;

[0290] each of the "Rj" represents the CH2-PO3H2 group;

[0291] “m” is an integer between 10 and 250;

[0292] “q” is an integer equal to 1 or 2;

[0293] “y” is an integer equal to 1 or 2, preferably equal to 1.

[0294] In particular, the polyalkoxylated phosphonate may be a polyalkoxylated phosphonate of formula (IV) in which "R5" is a methyl group, the "Ri" are ethylene and propylene groups, "m" being between 30 and 50, "r+q" is 1, "Q" is a propylene group, "A" is a methylene group, "y" is 1 and "Rj" corresponds to the CH2-PO3H2 group.

[0295] Preferably, the total mass content of the water-reducing adjuvant or high water reducer selected from polyalkoxylated phosphonates is between 30 and 40% by mass, preferably between 35% and 40% by mass, relative to the total dry mass (in active materials) of the adjuvant composition.

[0296] Preferably, the ratio between the total mass content of water-reducing adjuvant or high water-reducing agent selected from polyalkoxylated polycarboxylates and the total mass content of water-reducing adjuvant or high water-reducing agent selected from polyalkoxylated phosphonates is strictly greater than 1, preferably between 1.05 and 2.0, preferably between 1.05 and 1.9. Calcium salt

[0297] The adjuvant composition comprises a calcium salt in a mass content ranging from 0.1% to 15% by mass relative to the total dry mass (of active materials) of the adjuvant composition.

[0298] Preferably, the calcium salt is chosen from calcium chloride, calcium nitrate, calcium dihydroxide, calcium oxalate, calcium acetate, calcium thiocyanate, preferably the calcium salt is calcium nitrate or calcium dihydroxide.

[0299] Preferably, the mass content of calcium salt is between 1% and 13% by mass, preferably between 5% and 13% by mass, preferably between 7% and 13% by mass, relative to the total dry mass (of active materials) of the adjuvant composition. Antifoaming agents and / or air-entraining agents

[0300] The additive composition comprises at least one antifoaming agent and / or at least one air-entraining agent. Examples of antifoaming agents include ethoxylated fatty alcohols or amines, and these agents allow for modification of the air entrainment provided by the additive composition in the hydraulic composition. These antifoaming and / or air-entraining agents are preferably selected from among the commonly used antifoaming and / or air-entraining agents known to those skilled in the art.

[0301] Preferably, the adjuvant composition includes at least one antifoaming agent, and optionally at least one air-entraining agent.

[0302] Preferably, the mass content of antifoaming agent and / or air-entraining agent is from 0.3% to 2% by mass, preferably from 0.5% to 1% by mass, relative to the total dry mass of active materials of the adjuvant composition. Biocidal agents

[0303] The adjuvant composition comprises at least one biocidal agent, for example isothiazolinones. These molecules help to protect the adjuvant composition from bacterial contamination over time. These biocidal agents are preferably chosen from among the commonly used biocidal agents known to those skilled in the art.

[0304] Preferably, the mass content of biocidal agents is from 0.1% to 0.7% by mass, preferably from 0.2% to 0.5% by mass, relative to the total dry mass of active materials of the adjuvant composition. Adjuvant composition

[0305] Other additional additives may be used within the scope of the present invention in addition to the water-reducing agent(s) or high water-reducing agent(s) and the rheological agent(s). These additional additives may be selected by those skilled in the art from among the typical additives found in hydraulic binder compositions and hydraulic compositions.Examples include: carboxylic acids or their salts such as acetic, adipic, gluconic, oxalic, citric, maleic, lactic, tartaric, malonic acids and mixtures thereof; milling agents (including ethylene glycol oligomers or propylene glycol oligomers or mixtures thereof); setting retarders; hardening and setting accelerators such as glycerols, formic acid, lithium salts, aluminum salts, magnesium salts, sodium salts; alkanolamines and mixtures thereof; alkali-earth or aluminum salts; inorganic nanoparticles, for example silica or alumina nanoparticles, calcium carbonate nanoparticles, calcium hydrosilicate (HSC) nanoparticles, and mixtures thereof.

[0306] Preferably, the adjuvant composition further comprises 0 to 2% by mass, preferably 0.1% to 1% by mass of additional adjuvants, relative to the total dry mass of active materials of the adjuvant composition.

[0307] Preferably, the adjuvant composition further comprises an alkanolamine, preferably selected from diethanolisopropanolamine (DEIPA), triisopropanolamine (TIPA), N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA), triethanolamine (TEA), N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THEED) and methyldiethanolamine (MDEA), bis-(2-hydroxypropyl)-amine (DIPA) and diethanolamine (DEA), preferably the alkanolamine is diethanolisopropanolamine (DEIPA).

[0308] Preferably, the adjuvant composition is in the form of a liquid solution, a suspension, preferably aqueous, or a powder, and preferably is in the form of a liquid solution.

[0309] When the adjuvant composition is in powder form, it may further comprise an additional compound in powder form. This additional compound is preferably selected from ground calcium carbonate, precipitated calcium carbonate, silica, precipitated silica, calcium sulfate (anhydrous or hemihydrate or dihydrate), barium sulfate, granulated blast furnace slag, ground calcined or uncalcined clays, ground zeolite, silicates and aluminosilicates, talc, chalk, ground dolomite, ground expanded perlite, ground diatomite, the Ground calcined diatomite, ground recycled hardened cementitious materials (including foam concrete) and mixtures thereof. The composition may also include colorants.

[0310] When the adjuvant composition is in the form of a suspension or a liquid solution, it further comprises water. The suspension or liquid solution may also comprise dyes.

[0311] Throughout this description, the contents of the additive composition are stated relative to the total dry mass of active materials in the additive composition. "Regarding active materials" means that only those compounds that have an effect on a property of a hydraulic composition containing them are taken into account. Active materials or active compounds are to be distinguished from materials (powder or liquid) that are present in the additive composition solely as a diluent but have no noticeable effect on a property of a hydraulic composition containing them; they are therefore inert compounds. In particular, a content relative to the total dry mass of active materials means that water is not taken into account in the case of a composition in the form of a suspension or liquid solution, and that the additional compound(s) in powder form are not taken into account in the case of a composition in powder form.Advantageously, the contents are expressed in relation to the total mass content of water-reducing adjuvants or high water-reducing adjuvants chosen from polyalkoxylated polycarboxylates, water-reducing adjuvants or high water-reducing adjuvants chosen from polyalkoxylated phosphonates, rheological agent(s), calcium salt(s), antifoaming agent(s) and / or air-entraining agent(s), biocidal agent(s), and any additional colorants and / or additives. Hydraulic composition

[0312] The adjuvant composition according to the invention can be implemented in a hydraulic composition to provide an adjuvanted hydraulic composition.

[0313] The hydraulic composition with added additives comprises:

[0314] - a hydraulic binder composition,

[0315] - an adjuvant composition according to the invention,

[0316] - water,

[0317] - possibly an aggregate, and

[0318] - possibly a mineral addition.

[0319] The hydraulic composition is preferably a composition of concrete, mortar or screed.

[0320] The term "aggregates" means a collection of mineral grains with an average diameter of between 0 and 125 mm. According to their diameter, aggregates are classified into one of from the following six families: fillers, sands, gravels, crushed stone, and ballast (standards EN 12620 and EN 13242+A1). The most commonly used aggregates are:

[0321] - 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,

[0322] - sands with a diameter between 0 and 6.3 mm,

[0323] - bass drivers with a diameter greater than 6.3 mm,

[0324] - gravel with a diameter between 2 mm and 63 mm.

[0325] Sands are therefore included in the definition of aggregate according to the invention.

[0326] The fillers may in particular be of calcareous or dolomitic origin.

[0327] The term "mineral additions" means granulated blast furnace slag (as defined in EN 197-1:2011 paragraph 5.2.2), steelmaking slag, pozzolanic materials (as defined in EN 197-1:2011 paragraph 5.2.3), fly ash (as defined in EN 197-1:2011 paragraph 5.2.4), calcined shale (as defined in EN 197-1:2011 paragraph 5.2.5), or silica fume (as defined in EN 197-1:2011 paragraph 5.2.7 or EN 197-5:2021 paragraph 5), limestone or mixtures thereof.

[0328] The hydraulic composition may further include at least one additive as described above for the adjuvant composition.

[0329] Hydraulic binder composition

[0330] A hydraulic binder composition comprises at least one compound or mixture of compounds having the property of hydrating in the presence of water and whose hydration makes it possible to obtain a solid having mechanical characteristics.

[0331] The hydraulic binder composition may include, in particular, a cement according to EN 197-1 (2012), in particular a CEM I, CEM II, CEM III, CEM IV or CEM V cement; a cement according to EN 197-5 (2021), in particular a CEM ILC / M or CEM VI cement; a cement according to EN 197-6 (2023), a supersulfated cement according to EN 15743+A1 (2015).

[0332] The hydraulic binder composition may therefore include one or more mineral additions. The term "mineral additions" refers to slags (as defined in EN 197-1:2012 paragraph 5.2.2 and EN 15167-1:2006), steelmaking slags, pozzolanic materials (as defined in EN 197-1:2012 paragraph 5.2.3), fly ash (as defined in EN 197-1:2012 paragraph 5.2.4), calcined shale (as defined in EN 197-1:2012 paragraph 5.2.5), or silica fume (as defined in EN 197-1:2012 paragraph 5.2.7 or EN 197-5 paragraph 5), limestones or mixtures thereof.

[0333] The hydraulic binder composition may also include calcium sulfate, as defined in EN 197-1:2012 paragraph 5.4.

[0334] Preferably, the hydraulic binder composition has an amount of clinker less than or equal to 80% by mass, preferably from 0 to 80% by mass, relative to the total mass of the hydraulic binder composition.

[0335] The hydraulic binder composition therefore preferably comprises at least one mineral material other than clinker, and possibly clinker.

[0336] Preferably, the hydraulic binder composition comprises, relative to the total mass of the hydraulic binder composition, 20% to 100% by mass of a mineral material other than clinker, preferably 20% to 99.99% by mass, preferably 30% to 99% by mass, preferably 40% to 99% by mass, preferably 45% to 95% by mass, preferably 50% to 95% by mass, and preferably 60% to 90% by mass. If the hydraulic binder composition comprises several mineral materials other than clinker, these amounts correspond to the total content of mineral materials other than clinker.

[0337] When the hydraulic binder composition includes clinker, the clinker is present in a content ranging preferably from 0.01% to 80% by mass, preferably from 1% to 70% by mass, preferably from 1% to 60% by mass, preferably from 5% to 55% by mass, preferably from 5% to 50% by mass, preferably from 10% to 40% by mass, relative to the total mass of the hydraulic binder composition.

[0338] The clinker is in particular Portland or sulfoaluminate clinker, preferably Portland clinker as defined in the book "Cernent Chemistry". Harry FW Taylor. Edition, 2nd, Academy Press, 1990).

[0339] The mineral material other than clinker can be any material capable of forming part of the composition of a hydraulic binder.

[0340] Mineral materials other than clinker suitable for the present invention are, for example, calcium sulfates, mineral additions (such as calcined clays, limestones, natural or artificial pozzolans, silica fumes, fly ash, granulated blast furnace slags, calcined shales), crystallized, expanded, vitrified (granulated or pelletized) blast furnace slags, conversion steel slags, electric arc furnace carbon steel production slags, ladle slags, crushed shales, quartz, aluminous cements, sulfoaluminate cements, recycled glass, zeolites, diatomaceous earths, recycled concrete fines from deconstruction, and any mixture thereof.

[0341] In particular, the mineral material other than clinker is selected from calcium sulfates and mineral additions, more particularly from calcium sulfates, calcined clays, limestones, natural or artificial pozzolans, fly ash and blast furnace slags, and even more particularly from calcium sulfates, calcined clays, limestones, natural or artificial pozzolans, blast furnace slags, and any mixture thereof, advantageously among calcium sulfates, calcined clays, limestones, blast furnace slags, and any mixture thereof.

[0342] The hydraulic binder composition may in particular be as described in patent applications EP4330206A1, EP4330208A1, WO2024023065A1 or WO2024023066A1.

[0343] The expressions "from ... to ...", "between ... and ...", "ranging from ... to ...", "varies from ... to ...", and "less than ..." should be understood inclusive of limits, unless otherwise specified.

[0344] The invention will become clearer upon reading the following non-limiting examples.

[0345] EXAMPLE EXAMPLE 1#:

[0346] Evaluation of the performance of the adjuvant composition on a low-carbon hydraulic composition, with a specific ternary binder:

[0347] [Tables 1] Component Hydraulic Composition No. 1 0 / 4 mm crushed (kg / m3) 970 4 / 10 mm crushed (kg / m3) 399 10 / 20 mm crushed (kg / m3) 636 Ternary binder (kg / m3) 360 Effective water (kg / m3) 130 Combination of additives (kg / m3) 3.8 (0.280 polymer A, 0.093 polymer B, 0.117 polymer C, 0.459 polymer D, 0.120 calcium nitrate, 0.009 antifoam, 0.003 biocide, 2.719 water) Effective Water / Binder Ratio 0.36

[0348] The detailed composition of the ternary binder is as follows:

[0349] [Tables 2] Phase Proportion (%) Clinker 19.5 Calcium sulfate 2 Ground granulated blast furnace slag 29.5 Calcite 49 The combination of adjuvants used has the following composition (the contents are expressed as a percentage of the total dry mass of the active compounds in the combination of adjuvants): - 25.9% polymer A:

[0350]

[0351] (!) H^C with a = 65, b = 35 and z = 53, O

[0352] (he) z - 8.6% polymer B: (H)

[0353] with a = 49, b = 45, c = 6 and z = 17,

[0354] - 10.8% of polymer C: with a = 82.3, b = 17.7 and z = 53,

[0355] - 42.5% of polymer D: HO OH

[0356] with n=6, m=35, R = H or CH3 and the molar ratio PO / OE = 10 / 31,

[0357] - 11.1% calcium nitrate,

[0358] - 0.8% antifoams, of which 50% are alkyldimethylamine type and 50% are fatty alcohols ethoxylated, and

[0359] - 0.3% biocide, of the (ethylendioxy) dimethanol type.

[0360] Various rheological agents are added to the hydraulic composition of Table 1 and inverted cone measurements were carried out according to standard NF PI8-462 (2023) with filling in one go, without application of blows distributed on the surface of concrete.

[0361] The slump measurement was carried out according to standard NF EN 12350-2 (2019). The compressive strength measurement was carried out according to standard NF EN 12390-3 (2019) on 15x15x15cm3 cubic specimens after 24h wet curing (RH = 100%) in a mold in a room maintained at 20°C.

[0362] Determination of the dosage of rheological agent:

[0363] To determine the dosage of rheological agent required for the low carbon type hydraulic composition defined in Table 1, spread tests on the paste scale of the adjuvanted hydraulic composition were carried out.

[0364] The results of the spreading tests according to protocol A defined in the description are summarized in the following table (the dosages indicated in rheological agent correspond to the dosages of active material relative to the total mass of ternary binder):

[0365] [Tables3] Rheological agent used Spreading number Rheological agent dosage (% sec) Spreading (mm) sx / s0 High molecular weight polycarboxylate So 0.000% 410 100% Si 0.022% 300 73% s2 0.028% 270 66% s3 0.032% 255 62% s4 0.074% 235 57% s5 0.134% 225 55% Diuta gum So 0.0000% 410 100% Si 0.0005% 380 93% s2 0.0023% 350 85% s3 0.0034% 290 71% s4 0.0054% 290 71% Methyl hydroxyet hyl cellulose So 0.0000% 410 100% Si 0.0025% 410 100% s2 0.0050% 395 96% s3 0.0100% 375 91% s4 0.0200% 345 84%

[0366] It is observed that the use of a high molar mass polycarboxylate results in a reduction of spreading and is dependent on the dosage of the rheological agent. A dosage The presence of 0.032% high molecular weight polycarboxylate reduces the spreading of the paste in the adjuvanted hydraulic composition by 38%. Similarly, the use of diutan gum or methyl hydroxyethyl cellulose also reduces spreading, the amount of which depends on the concentration.

[0367] These various rheological agents were introduced into the hydraulic composition of Table 1 in different proportions. The proportions indicated for rheological agent correspond to the proportions relative to the total mass of ternary binder.

[0368] The results are summarized in the following table:

[0369] [Tables4] Compound Test A* Test B Test C Test D Test E Test F High-bulk polycarboxylate - 0.032% (0.1152 kg / m³) - - - - Diutan gum - - 0.0005% (0.0018 kg / m³) 0.0010% (0.0036 kg / m³) 0.0020% (0.0072 kg / m³) - Methyl hydroxyethyl cellulose - - - - - 0.010% (0.036 kg / m³) 5 min slump (mm) 225 230 235 235 230 220 30 min slump (mm) 230 230 230 230 230 220 60 min slump (mm) 210 220 210 210 210 215 Slump 90 min (mm) 205 220 195 195 185 175 Slump 120 min (mm) 200 215 180 155 155 160 Flow through inverted cone 5 min (s) 11.9 5.8 9.7 6.5 9.6 8.1 Flow through inverted cone 30 min (s) 10.3 5.2 10.5 6.9 9.3 7.9 Flow through inverted cone 60 min (s) 14.3 5.5 8.9 7.3 9.8 8.3 Flow through inverted cone 90 min (s) 10.6 4.9 8.7 6.1 9.0 7.8 Flow through inverted cone 120 min (s) - 7.7 9.1 6.4 9.2 6.7 Compressive strength at 24h (MPa) 6.9 6.5 6.6 6.8 6.7 7.1

[0370] * : comparative

[0371] Test G: same hydraulic composition as in Table 1 without polymers A to D + 0.032% (dry mass) of high-bulk polycarboxylate. Results: Slump at 5 min: 40 mm, Inverted cone flow at 5 min: not measurable

[0372] It is observed that the use of a high molar mass polycarboxylate (Test B) reduces the inverted cone flow time by half compared to the reference concrete (Test A). The addition of Diutan gum or Methyl hydroxyethyl cellulose also results in this reduction of the inverted cone flow time.

[0373] This result is surprising since the rheological agent alone drastically increases the viscosity of the hydraulic composition, making the flow of concrete through the cone impossible (test G). The rheological agent and the superplasticizers therefore act synergistically to improve the viscosity of the hydraulic composition over two hours of workability.

[0374] The addition of rheological agents has no impact on the compressive strengths measured at 24h and 20°C. EXAMPLE 2#:

[0375] Evaluation of the performance of the adjuvant composition on two low-carbon hydraulic compositions, with specific ternary binder, differing from the composition in Table 1 by the W / C ratio and the specific ternary binder content:

[0376] [Tables5] Hydraulic Composition Component No. 2 Hydraulic Composition No. 3 0 / 1 mm rolled (kg / m3) 215 250 0 / 4 mm crushed (kg / m3) 640 685 4 / 22.4 mm crushed (kg / m3) 905 950 Ternary binder (kg / m³) 350 280 Effective water (kg / m³) 148 126 Combination of additives (kg / m³) 2.975 (0.230 polymer A, 0.199 polymer B, 0.295 polymer D, 0.110 polymer E, 0.080 calcium nitrate, 0.006 antifoam, 0.003 biocide, 2.051 water) 4.116 (0.319 polymer A, 0.276 polymer B, 0.408 polymer D, 0.152 polymer E, 0.111 calcium nitrate, 0.009 antifoam, 0.004 biocide, 2.838 water) Effective water / binder ratio 0.42 0.45

[0377] The details of the composition of the specific ternary binder are presented in Table 2.

[0378] The combination of adjuvants used has the following composition (the contents are expressed by mass relative to the total dry mass of the active compounds in the combination of adjuvants):

[0379] - 24.9% polymer A: (f) H^C with a = 65, b = 35 and z = 53,

[0380] -21.55% of polymer B: HqC (0 ¢8)

[0381] with a = 49, b = 45, c = 6 and z = 17,

[0382] - 31.9% of polymer D: R HO OH

[0383] with n=6, m=35, R = H or CH3 and the molar ratio PO / OE = 10 / 31,

[0384] - 11.9% of polymer E: HCT (0 0. > z" (U b”)

[0385] with a = 43, b' = 16, b”= 41, z' = 53 and z” = 8.

[0386] - 8.7% calcium nitrate,

[0387] - 0.7% antifoams, of which 50% are alkyldimethylamine type and 50% are fatty alcohols ethoxylated, and

[0388] - 0.35% biocide, of the (ethylendioxy) dimethanol type.

[0389] In the same way as for the previous example, a high molar mass polycarboxylate type rheological agent was added to the two hydraulic compositions in Table 5 and inverted cone measurements were carried out according to standard NF P18-462 (2023) with filling in one pass, without application of blows distributed on the concrete surface.

[0390] The slump measurement was carried out according to standard NF EN 12350-2 (2019).

[0391] Determination of the dosage of rheological agent:

[0392] To determine the dosage of rheological agent required for the two low-carbon hydraulic compositions (No. 2 and No. 3) defined in Table 5, spread tests on the paste scale of the adjuvanted hydraulic composition were carried out.

[0393] The results of the spreading tests according to protocol A defined in the description are summarized in the following table (the dosages indicated in rheological agent correspond to the dosages of active material relative to the total mass of ternary binder):

[0394] [Tableauxô] Hydraulic Composition Spreading Number Rheological Agent Dosage (% dry) Spreading (mm) sx / s0 Hydraulic Composition No. 2 So 0.000% 390 100% Si 0.022% 280 72% s2 0.031% 230 62% s3 0.068% 230 59% Hydraulic Composition No. 3 So 0.0000% 420 100% If 0.022% 310 74% s2 0.054% 280 67% s3 0.068% 275 66%

[0395] In the case of hydraulic composition No. 2, a dosage of 0.031% rheological agent reduces the spread of the paste of hydraulic composition No. 2 by 38%. Conversely, a higher dosage of rheological agent (0.054%) is required to achieve a 33% reduction in the spread of the paste of hydraulic composition No. 3.

[0396] The dosages indicated in rheological agent correspond to the dosages relative to the total mass of ternary binder.

[0397] The results are summarized in the following table:

[0398] [Tables?] Test H* Test I Test J* Test K Hydraulic Composition No. 2 No. 2 No. 3 No. 3 High-mass polycarboxylate 0% 0.031% (0.110 kg / m³) 0% 0.054% (0.152 kg / m³) 5-min Slump (mm) 250 240 250 220 5-min Inverted Cone Flow (s) Not measurable - Total Segregation 1.2 Not measurable - Total Segregation 3.0

[0399] * : comparative

Claims

Demands

1. Adjuvant composition comprising, in relation to the total dry mass of active materials of the adjuvant composition: - 35% to 60% by mass of at least one water-reducing or high water-reducing adjuvant selected from polyalkoxylated polycarboxylates, - 25% to 45% by mass of at least one water-reducing or high water-reducing adjuvant selected from polyalkoxylated phosphonates, - 0.01% to 15% by mass of at least one rheological agent, - 0.1% to 15% by mass of a calcium salt, - 0.1% to 3% by mass of at least one antifoaming agent and / or at least one air-entraining agent, and - 0.05% to 1% by mass of biocidal agent(s).

2. Adjuvant composition according to claim 1, wherein the rheological agent is selected from: - polysaccharide gums, - celluloses and cellulose ethers, - high molecular weight polycarboxylates, - polyethylene glycols and polyethylene glycol monomethyl ether, - latexes, - polyacrylamides, - polyvinyl alcohols, - clays, - sodium alginates, and - any mixture thereof.

3. Adjuvant composition according to claim 1 or 2, wherein the total mass content of rheological agent is from 0.01% to 12% by mass, preferably from 0.02% to 10% by mass, preferably from 0.03% to 10% by mass, relative to the total dry mass of active materials) of the adjuvant composition.

4. Adjuvant composition according to any one of the preceding claims, wherein the polycarboxylate polyalkoxylated polymers comprise units of formulas (I) and (II), and optionally units of formula (III), as follows: in which: - “R2” and “R3” each independently represent a hydrogen or a methyl group, - "M" each independently represents H+ or a valence cation v chosen from an alkali metal cation, an alkaline earth metal cation, a divalent or trivalent metal cation, an ammonium cation or an organic ammonium cation, - when "M" represents H+, "v" represents 1, and when "M" represents a cation as defined above, "v" is the valence of the cation M, - “R7” and “R8” each independently represent a hydrogen, a methyl, or a group of the formula -COO(M)i / v, with M and v as defined above, - "m" represents 0, 1 or 2, - "p" represents 0 or 1, - "X" is O or NR9, "R9" representing H, a C1-C20 alkyl group, a cycloalkyl group, or an alkylaryl group, and - "RI" represents a C1-C20 alkyl group, a cycloalkyl group, an alkylaryl group, or -[Alkyl-O]z-R6, in which the "Alkyl" in each [Alkyl-O] unit independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, and "R6" represents H, a C20 Cl alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is an integer from 2 to 250, - "a" is a number ranging from 0.05 to 0.95, "a" being the mole fraction of formula (I) units in the polymer, - "b" is a number ranging from 0.05 to 0.95, "b" being the mole fraction of formula (II) units in the polymer,

5. - “L” represents a bonding group to the main chain of the polymer, and is in particular chosen from a direct bond, an oxygen atom, an -NR12- ​​group, R12 being a hydrogen or an alkyl group in Cl to C6, and an alkylene group in C2-C6, preferably L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom, - n = 0 or 1, and if n = 1, "W" is a spacer group, in particular a Cl-C2O alkylene group possibly substituted, or a group of formula -[Alkyl-O]t- in which the "Alkyl" of each [Alkyl-O] unit independently represents an alkylene group comprising 2 to 4 carbon atoms, and "t" is an integer ranging from 1 to 500, - "RIO" each independently represents a monovalent group, in particular chosen from a hydrogen, a C6 Cl alkyl group, and a group of formula -[Alkyl-O]t-R13 in the "Alkyl" of each unit [Alkyl-O] each independently represents an alkylene group of 2 to 4 carbon atoms, "t" is an integer ranging from 1 to 500 and "R13" is chosen from a hydrogen and a C3 Cl alkyl, or "RIO" is a cation, in particular an alkali, alkaline earth or ammonium cation; - "RI 1" is a monovalent group, in particular is chosen from a hydrogen atom, a hydroxyl group and an alkyl group in Cl to CIO, preferably "RI 1" is a hydroxyl group; and - "c" is a number from 0 to 0.15, "c" being the mole fraction of formula (III) units in the polymer. Adjuvant composition according to claim 4, wherein, in formula units (I) and (II), and (III) if present, polycarboxylate polyalkoxylated polymers: - “R2” represents H, - "R3" independently represents either a hydrogen or a methyl group, - "M" is H, sodium or calcium, preferably H, - "a" is a number ranging from 0.20 to 0.90, preferably "a" is a number ranging from 0.40 to 0.85, - “R7” represents H, - "R8" independently represents a hydrogen or a methyl group, -X = O, - RI = -[Alkyl-O]z-R6, preferably with: - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-CHMe-, -CHMe-CH2-, and / or - at least 80% of the "Alkyl" in the group -[Alkyl-O]z- represent -CH2-CH2-, or even all the "Alkyl" in the group -[Alkyl-O]z- represent -CH2-CH2-, and / or - "z" represents an integer from 5 to 200, in particular from 10 to 100, preferably from 25 to 75, and / or - "R6" represents H or Me, - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, - "b" is a number from 0.10 to 0.80, preferably "b" is a number from 0.15 to 0.60, -n = 0, - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom, - "RIO" each independently represents a hydrogen, a C1-C6 alkyl group, or "RIO" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably RIO is a hydrogen, - "RI 1" is a hydroxyl group, and - "c" is a number from 0 to 0.12, preferably from 0 to 0.

10.

6. Adjuvant composition according to any one of the preceding claims, wherein the total mass content of water-reducing or high water-reducing adjuvant selected from polyalkylated polycarboxylates is from 40% to 60% by mass, preferably from 44% to 55% by mass, relative to the total dry mass of active materials of the adjuvant composition.

7. An adjuvant composition according to any one of the preceding claims, wherein the polyalkoxylated phosphonate polymers have the following formula (IV): . ■ ■ / [RS--G(R j—O ““““ N in which: - "R5" is a hydrogen atom or a monovalent hydrocarbon group comprising from 1 to 18 carbon atoms and possibly one or more heteroatoms; - the "Ri"s are similar or different from each other and represent an alkylene such as ethylene, propylene, butylene, amylene, octylene or cyclohexene, or an arylene such as styrene or methylstyrene, the "Ri"s possibly containing one or more heteroatoms; - "Q" is a hydrocarbon group comprising from 2 to 18 carbon atoms and possibly one or more heteroatoms; - "A" is an alkylene group comprising from 1 to 5 carbon atoms;- the "Rj" are similar or different from each other and can be chosen from: - the group A-PO3H2, A having the aforementioned meaning, - an alkyl group comprising from 1 to 18 carbon atoms and which can bear [R5-O(Ri-O)m] groups, R5 and Ri having the aforementioned meanings, - "m" is a number greater than or equal to 0, - "r" is the number of [R5-O(Ri-O)m] groups borne by the set of Rj, - "q" is the number of [R5-O(Ri-O)m] groups borne by Q, the sum "r+q" is between 1 and 10, - "y" is an integer between 1 and 3, - "Q", "N" and the "Rj" can together form one or more rings, this or these rings may in addition contain one or more other heteroatoms.;

8. Adjuvant composition according to any one of the preceding claims, wherein the total mass content of water-reducing or high water-reducing adjuvant selected from polyalkoxylated phosphonates is between 30 and 40% by mass, preferably between 35% and 40% by mass, relative to the total dry mass of active materials of the adjuvant composition.

9. Adjuvant composition according to any one of the preceding claims, wherein the ratio between the total mass content of water-reducing or high-strength water-reducing adjuvant selected from polyalkylated polycarboxylates and the total mass content in water reducing adjuvant or high water reducing agent chosen from among the polyalkoxylated phosphonates is strictly greater than 1, preferably between 1.05 and 2.0, preferably between 1.05 and 1.

9.

10. Adjuvant composition according to any one of the preceding claims, wherein the calcium salt is selected from calcium chloride, calcium nitrate, calcium dihydroxide, calcium oxalate, calcium acetate, calcium thiocyanate, preferably the calcium salt is calcium nitrate or calcium dihydroxide.