Additive composition for hydraulic compositions with reduced clinker content

Abstract

The present invention relates to an additive composition comprising, in relation to the total dry mass of the additive composition: - from 35% to 60% by mass of at least one water-reducing or high water-reducing additive chosen from polyalkoxylated polycarboxylates, - from 25% to 45% by mass of at least one water-reducing or high water-reducing additive chosen from 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).

Description

[0001] Composition of admixtures for hydraulic compositions with reduced clinker content

[0002] The present invention relates to an additive composition intended in particular for hydraulic compositions with reduced clinker content.

[0003] 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 decrease their carbon footprint.

[0004] One obstacle 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. This reduction is necessary to promote strength development at all ages, particularly in the short term, and to avoid impacting the structure's durability. This decrease 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 contribute to this increased viscosity, as the water demand of some mineral additives is higher than that of conventional cements containing high proportions of clinker.

[0005] Most of the additives 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 too high to be economically viable.

[0006] There is therefore a need for new additive compositions that can effectively reduce the viscosity of hydraulic compositions, especially those with reduced clinker content.

[0007] To this end, the invention relates to an 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 chosen from polyalkyl polycarboxylates, 25% to 45% by mass of at least one water-reducing or high water-reducing adjuvant chosen from polyalkyl 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).

[0008] The inventors have indeed discovered, surprisingly, that the addition of a rheological agent, known in principle to increase the viscosity of hydraulic compositions, actually reduces their viscosity when combined 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.

[0009] Rheological agent

[0010] The adjuvant composition according to the invention comprises at least one rheological agent.

[0011] The rheological agents of the invention are preferably compounds capable of increasing the yield stress of the paste in a hydraulic composition and / or the viscosity of the paste in a hydraulic composition. These agents are therefore compounds that, in particular, decrease the flow rate of a hydraulic composition containing them.

[0012] It should be noted that the range of rheological agent 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 according to the nature of the rheological agent(s). This dosage ultimately determines the rheological agent content of the additive composition.

[0013] Preferably, the rheological agent(s) and the dosages associated with each rheological agent in a hydraulic composition already modified with additives, notably one or more reducing or high-strength water-reducing agents and any other additives (excluding rheological agents) (referred to as the "admixed hydraulic composition under study" in the remainder of Protocol A), is / are determined by means of a series of smear measurements using a Schmidt ring (cylinder with an internal diameter of 60 mm and a height of 50 mm) on a 141 mL volume 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%:

[0014] - Preparation of an additive paste by mixing, using a Rayneri mixer equipped with a 350 mm shaft length, 8 mm shaft diameter, and 80 mm disc diameter, at 500 rpm for TO+4 minutes: water, a hydraulic binder composition, one or more reducing agents or high-reducing water agents, and any other additives in the hydraulic binder composition under study. The hydraulic binder composition, the water / binder ratio, the reducing agents or high-reducing water agents and any other additives, and the quantity of reducing agents or high-reducing water agents and any other additives are those of the hydraulic binder composition under study. This additive paste is named Po; TO corresponds to the first contact between the water and the hydraulic binder composition.

[0015] - Filling the Schmidt ring with a volume of 141 mL of adjuvanted paste Po

[0016] - At T0+5min: Measurement of the spread over two perpendicular diameters after lifting the cone;

[0017] - The initial spreading value of the paste Po corresponds to the reference value without rheological agent (So);

[0018] - Perform the same test on other pastes Si, S2, ... S x presenting different dosages of 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;

[0019] - Each spread obtained is noted Si , S2, ... Sx, x being the last dosage evaluated.

[0020] - The required dosage is obtained when a measured spread value is 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%.

[0021] Preferably, the rheological agent is chosen from:

[0022] - polysaccharide gums, for example diutan gums, xanthan gums, welan gums, guar gums and guar ethers, including hydroxyethyl guar, hydroxypropyl guar and carboxymethyl guar, gellan gums, starch and starch ethers,

[0023] - Cellulose and cellulose ethers, including the alkyl, hydroxyalkyl and carboxyalkyl families, - 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,

[0024] - polyethylene glycol (PEG) and polyethylene glycol monomethyl ether (MPEG), preferably with a molar mass greater than 100,000 g / mol,

[0025] - latexes, for example those of the methacrylic copolymer and ethyl acrylate ester type,

[0026] - polyacrylamides,

[0027] - polyvinyl alcohols,

[0028] - clays, for example sepiolite and bentonite type clays,

[0029] - sodium alginates, and

[0030] - any one of their mixtures.

[0031] Preferably, the rheological agent is chosen from:

[0032] - polysaccharide gums, for example diutan gums, xanthan gums, welan gums, guar gums and guar ethers, including hydroxyethyl guar, hydroxypropyl guar and carboxymethyl guar, gellan gums, starch and starch ethers,

[0033] - celluloses and cellulose ethers, including the alkyl, hydroxyalkyl and carboxyalkyl families,

[0034] - 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

[0035] - any one of their mixtures.

[0036] Preferably, 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 positions 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 positions C1 to C12, vinyl and (meth)acrylic acid copolymers, vinyl and O1 to O12 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.Preferably, 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, preferably from 0.04% to 10% by mass, relative to the total dry mass (of 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 rheological agents, relative to the total dry mass (of active materials) of the adjuvant composition.

[0038] Water-reducing admixture or high-strength water reducer selected from polycarboxylate polyalkoxylates

[0039] The adjuvant composition of the invention comprises at least one water-reducing or high-water-reducing adjuvant selected from polycarboxylate polyalkoxylated polymers.

[0040] Preferably, polycarboxylate polyalkoxylated polymers comprise units of formulas (I) and (II), and optionally units of formula (III), as follows: in which

[0041] - “R2” and “R3” each independently represent a hydrogen or a methyl group,

[0042] - "M" represents each independently H + or a cation of valence 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,

[0043] - when "M" represents H + , "v" represents 1 , and when "M" represents a cation as defined above, "v" is the valence of the cation M,

[0044] - “R7” and “R8” each independently represent a hydrogen, a methyl or a group of formula -COO(M)i / v with M and v as defined above,

[0045] - "m" represents 0, 1 or 2,

[0046] - "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

[0047] - “R1” represents a C1-C20 alkyl group, a cycloalkyl group, an alkylaryl group, or -[Alkyl-O] z -R6, in which the "Alkyl" of each unit [Alkyl-O] independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, and "R6" represents H, a C1-C20 alkyl group, a cyclohexyl group, or an alkylaryl group, and "z" is an integer from 2 to 250,

[0048] - "a" is a number ranging from 0.05 to 0.95, "a" being the mole fraction of formula (I) units in the polymer,

[0049] - "b" is a number ranging from 0.05 to 0.95, "b" being the mole fraction of formula (II) units in the polymer,

[0050] - “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 R11 group), an oxygen atom, an -NR12- ​​group, R12 being a hydrogen or an alkyl group in C1 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,

[0051] - n = 0 or 1, and if n = 1, "W" is a spacer group, in particular an alkylene group in C1 to 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 C1 to C6,

[0052] - "R10" each independently represents a monovalent group, in particular chosen from a hydrogen, an alkyl group in C1 to C6, 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 an alkyl in C1 to C3, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation (and then the last O of the -[Alkyl-O]t group t is O');

[0053] - "R11" is a monovalent group, in particular is chosen from a hydrogen atom, a hydroxyl group and an alkyl group in C1 to C10, preferably "R11" is a hydroxyl group; and

[0054] - "c" is a number from 0 to 0.15, where "c" is the mole fraction of formula (III) units in the polymer. 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 be different from each other from one polymer unit to another.

[0055] Preferably, polycarboxylate polyalkoxylated polymers have a comb-like structure.

[0056] The following embodiments for formulas (I), (II) and (III) of the polycarboxylate polyalkoxylated polymer units may be considered independently or combined with each other in any combination:

[0057] - “R2” represents H, and / or

[0058] - "R 7" represents H, and / or

[0059] - "R3" each independently represents a hydrogen or a methyl, and / or

[0060] - "R8" each independently represents a hydrogen or a methyl, and / or

[0061] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, and / or

[0062] - X = O, and / or

[0063] - R1 = -[Alkyl-O] z -R6, preferably with:

[0064] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0065] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0066] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 25 to 75, and / or

[0067] - “R6” represents H or Me, and / or

[0068] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation preferably being 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 preferably being an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0069] - "a" is a number from 0.20 to 0.90, preferably "a" is a number from 0.40 to 0.85, and / or

[0070] - "b" is a number from 0.10 to 0.80, preferably "b" is a number from 0.15 to 0.60, and / or

[0071] - n = 0, and / or - L is an oxygen atom, and / or

[0072] - “R10” is hydrogen, and / or

[0073] - “R11” is a hydroxyl group, and / or

[0074] - "c" is a number ranging from 0 to 0.12, preferably from 0 to 0.10.

[0075] Preferably, in units of formula (I):

[0076] - “R2” represents H,

[0077] - "R3" each independently represents a hydrogen or a methyl group,

[0078] - "M" is H, sodium or calcium, preferably H,

[0079] - "a" is a number ranging from 0.20 to 0.90, preferably "a" is a number ranging from 0.40 to 0.85.

[0080] Preferably, in units of formula (II):

[0081] - “R7” represents H,

[0082] - "R8" each independently represents a hydrogen or a methyl group,

[0083] - X = O,

[0084] - R1 = -[Alkyl-O] z -R6, preferably with:

[0085] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0086] - at least 80% of the "Alkyl" group -[Alkyl-O] z - represent -CH2-CH2-, or even all the "Alkyl" of the group — [Alkyl-O] z - represent -CH2-CH2-, and / or

[0087] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 25 to 75, and / or

[0088] - "R6" represents H or Me,

[0089] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, and

[0090] - "b" is a number from 0.10 to 0.80, preferably "b" is a number from 0.15 to 0.60.

[0091] Preferably, in the units of formula (III) (if present):

[0092] - n = 0,

[0093] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom,

[0094] - "R10" each independently represents a hydrogen, a C1-C6 alkyl group, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably R10 is a hydrogen,

[0095] - "R11" is a hydroxyl group, and - "c" is a number from 0 to 0.12, preferably from 0 to 0.10.

[0096] According to one embodiment, "c" = 0. In other words, the polymer does not include formula units (III).

[0097] According to one embodiment (M1), the formula units (II) of the polycarboxylate polyalkoxylated polymers are such that p = 0 and m = 1 or 2, preferably 1, and "c" = 0.

[0098] Preferably, according to this embodiment (M1):

[0099] - “R2” represents H, and / or

[0100] - "R 7" represents H, and / or

[0101] - "R3" each independently represents a hydrogen or a methyl, preferably R3 = H and / or

[0102] - "R8" each independently represents a hydrogen or a methyl group, preferably R8 = Me, and / or

[0103] - X = O, and / or

[0104] - R1 = -[Alkyl-O] z -R6, preferably with:

[0105] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0106] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0107] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 25 to 75, and / or

[0108] - "R6" represents H or Me, preferably "R6" represents H, and / or

[0109] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation preferably being 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 preferably being an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0110] - "a" is a number from 0.30 to 0.95, preferably a is a number from 0.50 to 0.90, and / or

[0111] - "b" is a number from 0.05 to 0.70, preferably b is a number from 0.10 to 0.50.

[0112] Preferably, according to (M1):

[0113] - "R2" represents H, - "R3" represents each independently H or a methyl group, advantageously H,

[0114] - "M" is H, sodium or calcium, preferably H,

[0115] - "R 7" represents H,

[0116] - "R8" represents each independently H or a methyl group, advantageously a methyl group,

[0117] - X = O,

[0118] - R1 = -[Alkyl-O] z -R6, preferably with:

[0119] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-

[0120] CHMe-, -CHMe-CH2-, and / or

[0121] - at least 80% of the "Alkyl" group — [Alkyl-O] z- represent -CH2-CH2-, or even all the Alkyls of the group — [Alkyl-O] z - represent -CH2-CH2-, and / or

[0122] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 25 to 75, and / or

[0123] - "R6" represents H or Me, preferably "R6" represents H.

[0124] - "a" is a number from 0.30 to 0.95, preferably "a" is a number from 0.50 to

[0125] 0.90, and

[0126] - "b" is a number from 0.05 to 0.70, preferably "b" is a number from 0.10 to 0.50.

[0127] According to another embodiment (M2), the formula units (II) of the polycarboxylate polyalkoxylated polymers are such that p = 1 and m = 0.

[0128] Preferably, according to this embodiment (M2):

[0129] - “R2” represents H, and / or

[0130] - “R7” represents H, and / or

[0131] - "R3" each independently represents a hydrogen or a methyl, and / or

[0132] - "R8" each independently represents a hydrogen or a methyl, and / or

[0133] - X = O, and / or

[0134] - R1 = -[Alkyl-O] z -R6, preferably with:

[0135] - "Alkyl" represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2-

[0136] CHMe-, -CHMe-CH2-, and / or

[0137] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0138] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 50, and / or

[0139] - "R6" represents H or Me, preferably R6 represents Me, and / or

[0140] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation preferably being 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 preferably being an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0141] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or

[0142] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0143] - n = 0, and / or

[0144] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom,

[0145] - "R10" each independently represents a hydrogen, a C1-C6 alkyl group, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably R10 is a hydrogen,

[0146] - “R11” is a hydroxyl group, and

[0147] - "c" is a number ranging from 0 to 0.12, preferably from 0 to 0.10.

[0148] Preferably, according to (M2):

[0149] - “R2” represents H,

[0150] - "R3" represents each independently either an H or a methyl group,

[0151] - "M" is H, sodium or calcium, preferably H,

[0152] - “R7” represents H,

[0153] - "R8" represents each independently H or a methyl group,

[0154] - X = O,

[0155] - R1 = -[Alkyl-O] z -R6, preferably with:

[0156] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0157] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0158] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 50, and / or

[0159] - "R6" represents H or Me, preferably "R6" represents Me.

[0160] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60,

[0161] - L is an oxygen atom,

[0162] - "R10" is hydrogen,

[0163] - “R11” is a hydroxyl group,

[0164] - "c" is a number ranging from 0 to 0.12, preferably from 0 to 0.10.

[0165] 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).

[0166] 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.

[0167] According to this alternative (M2-1),

[0168] - “R2” represents H, and / or

[0169] - “R7” represents H, and / or

[0170] - "R3" each independently represents a hydrogen or a methyl group, preferably a methyl group, and / or

[0171] - "R8" each independently represents a hydrogen or a methyl group, preferably a methyl group, and / or

[0172] - X = O, and / or

[0173] - R1 = -[Alkyl-O] z -R6, preferably with:

[0174] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0175] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0176] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 50, and / or

[0177] - "R6" represents H or Me, preferably R6 represents Me, and / or

[0178] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation preferably being chosen from an ammonium salt N H4 +, 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 preferably being an alkaline earth metal cation, such as a magnesium or calcium ion, and / or - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or

[0179] - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0180] - n = 0, and / or

[0181] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom,

[0182] - "R10" each independently represents a hydrogen, a C1-C6 alkyl group, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably R10 is a hydrogen,

[0183] - “R11” is a hydroxyl group, and

[0184] - "c" is a number ranging 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.

[0185] According to another embodiment (M3), the units of formula (II) are present in the form of two distinct subunits (llb') and (llb”). Both subunits (llb') and (I Ib”) are of formula (II), according to any embodiment of the units of formula (II) defined above, but are different from each other. The units (I), and (III) if present, are according to any embodiment defined above.

[0186] 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 (llb') 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 (llb") in the polymer.

[0187] Preferably, according to this embodiment, "c" = 0. Preferably, the polymer therefore does not include (III) units.

[0188] Preferably, in the units (llb'):

[0189] - “R7” represents H,

[0190] - "R8" each independently represents a hydrogen or a methyl, preferably R8 = Me,

[0191] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, preferably p = 0 and m = 1,

[0192] - X = O, - R1 = -[Alkyl-0] z -R6, preferably with:

[0193] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0194] - at least 80% of the Alkyl group — [Alkyl-O] z - represent -CH2-CH2-, or even all the Alkyls of the group — [Alkyl-O] z - represent -CH2-CH2-, and / or

[0195] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 50, alternatively from 30 to 60, and / or

[0196] - "R6" represents H or Me, preferably "R6" represents H.

[0197] - "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 formula units (I lb') in the polymer.

[0198] Preferably, in the units (Il b”):

[0199] - “R7” represents H,

[0200] - "R8" each independently represents a hydrogen or a methyl, preferably R8 = H,

[0201] - either p = 0 and m = 1 or 2, preferably 1, or p = 1 and m = 0, preferably p = 1 and m = 0,

[0202] - X = O,

[0203] - R1 = -[Alkyl-O] z -R6, preferably with:

[0204] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0205] - at least 80% of the Alkyl group — [Alkyl-O] z - represent -CH2-CH2-, or even all the Alkyls of the group — [Alkyl-O] z - represent -CH2-CH2-, and / or

[0206] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 30, alternatively from 5 to 15, and / or

[0207] - "R6" represents H or Me, preferably "R6" represents Me.

[0208] - "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 formula units (II b") in the polymer.

[0209] 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.

[0210] More preferably, the water-reducing or high-strength water-reducing adjuvant chosen from among the polyalkyl polycarboxylates comprises a mixture:

[0211] - of at least one polycarboxylate polyalkoxylated polymer comprising units of formulas (I) and (II) in which p = 0, m = 1 and c = 0 according to any corresponding embodiment defined above, preferably according to embodiment (M1) as described above,

[0212] - 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.

[0213] Advantageously, the water-reducing or high-reducing adjuvant chosen from among the polyalkyl polycarboxylates comprises a mixture:

[0214] - 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,

[0215] - 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 (M1) as described above, and

[0216] - of a third 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.

[0217] Even more advantageously:

[0218] - the first polycarboxylate polyalkoxylated polymer is such that "a" is a number of

[0219] 0.30 to 0.70, preferably "a" is a number from 0.50 to 0.70, and "b" is a number of

[0220] 0.25 to 0.70, preferably "b" is a number from 0.30 to 0.60,

[0221] - 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.

[0222] Preferably, the first and second polycarboxylate polyalkoxylated polymers differ only in the value of "a" and "b".

[0223] Thus, preferably in the first and second polycarboxylate polyalkoxylated polymers:

[0224] - “R2” represents H,

[0225] - "R3" represents each independently H or a methyl group, advantageously H,

[0226] - "M" is H, sodium or calcium, preferably H,

[0227] - "R7" represents H, - "R8" each independently represents H or a methyl group, advantageously a methyl group.

[0228] - X = O,

[0229] - R1 = -[Alkyl-O] z -R6, preferably with:

[0230] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0231] - at least 80% of the "Alkyl" group — [Alkyl-O] z - represent -CH2-CH2-, or even all the Alkyls of the group — [Alkyl-O] z - represent -CH2-CH2-, and / or

[0232] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 25 to 75, and / or

[0233] - "R6" represents H or Me, preferably "R6" represents H.

[0234] Preferably, in the third polymer, polycarboxylate polyalkoxylated polymer:

[0235] - “R2” represents H, and / or

[0236] - “R7” represents H, and / or

[0237] - "R3" each independently represents a hydrogen or a methyl group, preferably a methyl group, and / or

[0238] - "R8" each independently represents a hydrogen or a methyl group, preferably a methyl group, and / or

[0239] - X = O, and / or

[0240] - R1 = -[Alkyl-O] z -R6, preferably with:

[0241] - “Alkyl” represents -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH2-CH2-CH2-, -CH2- CHMe-, -CHMe-CH2-, and / or

[0242] - at least 80% of the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, or even all the Alkyls of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or

[0243] - "z" represents an integer from 5 to 200, specifically from 10 to 100, preferably from 15 to 50, and / or

[0244] - "R6" represents H or Me, preferably R6 represents Me, and / or

[0245] - "M" represents H or a monovalent or divalent cation, "m" then representing 1 or 2, the monovalent cation preferably being 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 preferably being an alkaline earth metal cation, such as a magnesium or calcium ion, and / or

[0246] - "a" is a number from 0.30 to 0.80, preferably "a" is a number from 0.40 to 0.70, and / or - "b" is a number from 0.20 to 0.70, preferably "b" is a number from 0.30 to 0.60, and / or

[0247] - n = 0, and / or

[0248] - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom,

[0249] - "R10" each independently represents a hydrogen, a C1-C6 alkyl group, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably R10 is a hydrogen,

[0250] - “R11” is a hydroxyl group, and

[0251] - "c" is a number ranging 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.

[0252] Alternatively, the second polycarboxylate polyalkoxylated polymer can be according to embodiment (M3) as described above, in which the formula units (II) are present as two distinct subunits (IIb') and (IIb"). The first and third polycarboxylate polyalkoxylated polymers remain as defined above.

[0253] Preferably, the total mass content of water-reducing adjuvant or high water reducer chosen from polycarboxylate polyalkoxylated products 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.

[0254] If the adjuvant composition includes several (at least two) water-reducing or high-reducing adjuvants chosen from polyalkyl polycarboxylates, the above content ranges therefore refer to the total content of all the water-reducing or high-reducing adjuvants chosen from polyalkyl polycarboxylates, relative to the total dry mass (of active substances) of the adjuvant composition.

[0255] 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 (of active materials) of the adjuvant composition.

[0256] 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.

[0257] In particular, the mass content of the third polyalkyloxylated polycarboxylate polymer ranges from 5% to 20% by mass, preferably from 8% to 20% by mass, relative to the total dry mass (of active ingredients) of the adjuvant composition. The adjuvant is a water-reducing or high-strength water-reducing agent selected from among the polyalkyloxylated phosphonates.

[0258] The adjuvant composition of the invention comprises at least one water-reducing or high-water-reducing adjuvant selected from polyalkoxylated phosphonates.

[0259] Preferably, the polyalkoxylated phosphonate polymers have the following formula (IV): in which

[0260] - "R5" is a hydrogen atom or a monovalent hydrocarbon group comprising 1 to 18 carbon atoms and possibly one or more heteroatoms;

[0261] - the "Ri" 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;

[0262] - “Q” is a hydrocarbon group comprising 2 to 18 carbon atoms and possibly one or more heteroatoms;

[0263] - "A" is an alkylene group consisting of 1 to 5 carbon atoms;

[0264] - The "Rj" values ​​are similar or different from each other and can be chosen from:

[0265] - the group A-PO3H2, A having the aforementioned meaning,

[0266] - an alkyl group comprising from 1 to 18 carbon atoms and capable of bearing [R5-O(Ri-O)] groups m ], R5 and Ri having the aforementioned meanings,

[0267] - "m" is a number greater than or equal to 0,

[0268] - "r" is the number of groups [R5-O(Ri-O) m supported by all the RJs,

[0269] - "q" is the number of groups [R5-O(Ri-O) m carried by Q, the sum

[0270] - "r+q" is between 1 and 10,

[0271] - "y" is an integer between 1 and 3,

[0272] - “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.

[0273] 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.

[0274] Preferably, the polyalkoxylated phosphonate is a compound of formula (IV) in which:

[0275] "R5" is a hydrogen atom or a monovalent hydrocarbon group, saturated or unsaturated, comprising from 1 to 8 carbon atoms and possibly one or more heteroatoms; the "Ri" represent ethylene or propylene or a mixture of ethylene or propylene, preferably from 60% to 100% of the "Ri" are ethylene groups;

[0276] “Q” is a hydrocarbon group consisting of 2 to 8 carbon atoms and, possibly, one or more heteroatoms;

[0277] “A” is the methylene group; each of the “Rj” represents the CH2-PO3H2 group;

[0278] "m" is an integer between 10 and 250;

[0279] "q" is an integer equal to 1 or 2;

[0280] "y" is an integer equal to 1 or 2, preferably equal to 1.

[0281] In particular, the polyalkoxylated phosphonate can 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.

[0282] Preferably, the total mass content of water-reducing or high-water-reducing adjuvant chosen 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.

[0283] Preferably, the ratio between the total mass content of water-reducing adjuvant or high water reducer selected from polyalkoxylated polycarboxylates and the total mass content of water-reducing adjuvant or high water reducer selected from polyalkoxylated phosphonates is strictly greater than 1, preferably between 1.05 and 2.0, preferably between 1.05 and 1.9.

[0284] Calcium salt The adjuvant composition includes 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.

[0285] 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.

[0286] 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.

[0287] Antifoaming agents and / or air-entraining agents

[0288] The additive composition includes 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 modify the air entrainment provided by the additive composition in the hydraulic composition. These antifoaming and / or air-entraining agents are preferably chosen from among the commonly used antifoaming and / or air-entraining agents known to those skilled in the art.

[0289] Preferably, the adjuvant composition includes at least one antifoaming agent, and possibly at least one air-entraining agent.

[0290] 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 in the adjuvant composition.

[0291] Biocidal agents

[0292] The adjuvant composition includes at least one biocidal agent, for example, isothiazolinones. These molecules help protect the adjuvant composition from bacterial contamination over time. These biocidal agents are preferably chosen from among those commonly used and known to those skilled in the art.

[0293] 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 in the adjuvant composition.

[0294] Adjuvant Composition: Other additional adjuvants may be used within the scope of the present invention in addition to the water-reducing agent(s) or high-strength water-reducing agent(s) and the rheological agent(s). These additional adjuvants may be selected by those skilled in the art from among the typical adjuvants used 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.

[0295] 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 in the adjuvant composition.

[0296] 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).

[0297] 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.

[0298] When the admixture composition is in powder form, it may also include 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, 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, ground calcined diatomite, ground recycled hardened cementitious materials (including foam concrete), and mixtures thereof. The composition may also include colorants. When the admixture composition is in the form of a suspension or liquid solution, it also includes water. The suspension or liquid solution may also include dyes.

[0299] Throughout this description, the contents of the additive composition are given relative to the total dry mass of active ingredients in the additive composition. "Regarding active ingredients" means that only those compounds that affect a property of the hydraulic composition containing them are taken into account. Active ingredients or active compounds are distinct 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 the hydraulic composition containing them; these are therefore inert compounds. In particular, a content relative to the total dry mass of active ingredients means that water is not included in the case of a composition in suspension or liquid solution form, and that any additional compound(s) in powder form are not included in the case of a powder composition.Advantageously, the contents are expressed in relation to the total mass content of water reducing agents or high water reducing agents chosen from polyalkyl polycarboxylates, water reducing agents or high water reducing agents chosen from polyalkyl 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.

[0300] Hydraulic composition

[0301] The adjuvant composition according to the invention can be implemented in a hydraulic composition to provide an adjuvanted hydraulic composition.

[0302] The hydraulic additive composition includes:

[0303] - a hydraulic binder composition,

[0304] - an adjuvant composition according to the invention,

[0305] - water,

[0306] - possibly an aggregate, and

[0307] - possibly a mineral supplement.

[0308] The hydraulic composition is preferably a composition of concrete, mortar or screed.

[0309] The term "aggregates" refers to a collection of mineral grains with an average diameter between 0 and 125 mm. Based on their diameter, aggregates are classified into one of the following six categories: fillers, fine sands, sands, gravels, crushed stone, and ballast (standards EN 12620 and EN 13242+A1). The most commonly used aggregates are: fillers, which have a diameter of less than 2 mm and for which at least 85% of the aggregates have a diameter of less than 1.25 mm and at least 70% of the aggregates have a diameter of less than 0.063 mm; sands with a diameter between 0 and 6.3 mm; gravels with a diameter greater than 6.3 mm; and crushed stone with a diameter between 2 mm and 63 mm.

[0310] Sands are therefore included in the definition of aggregate according to the invention.

[0311] The fillers can notably be of limestone or dolomitic origin.

[0312] The term "mineral additions" refers to granulated blast furnace slag (as defined in EN 197-1:2011 paragraph 5.2.2), steelmaking slag, and pozzolanic materials (as defined in EN 197-1:2011 paragraph 5.2.2).

[0313] 5.2.3), fly ash (as defined in standard EN 197-1:2011 paragraph

[0314] 5.2.4), calcined shale (as defined in standard EN 197-1:2011 paragraph

[0315] 5.2.5), or silica fumes (as defined in standard EN 197-1:2011 paragraph 5.2.7 or standard EN 197-5:2021 paragraph 5), limestones or mixtures thereof.

[0316] The hydraulic composition may further include at least one additive as described above for the adjuvant composition.

[0317] Composition of hydraulic binder

[0318] 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.

[0319] The hydraulic binder composition may include, in particular, a cement conforming to standard EN 197-1 (2012), specifically a CEM I, CEM II, CEM III, CEM IV or CEM cement

[0320] V; a cement conforming to standard EN 197-5 (2021), in particular a CEM II-C / M or CEM cement

[0321] VI; a cement according to standard EN 197-6 (2023), a super-sulfated cement according to standard EN 15743+A1 (2015).

[0322] The composition of hydraulic binder 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), steel 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.

[0323] The hydraulic binder composition may also include calcium sulfate, as defined in standard EN 197-1:2012 paragraph 5.4.

[0324] 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.

[0325] The hydraulic binder composition therefore preferably includes at least one mineral material other than clinker, and possibly clinker.

[0326] 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.

[0327] When the hydraulic binder composition includes clinker, the clinker is present in a content preferably ranging 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.

[0328] The clinker is in particular Portland or sulfoaluminate clinker, preferably Portland clinker as defined in the book "Cement Chemistry" (Harry FW Taylor, 2nd edition, Academy Press, 1990).

[0329] The mineral material other than clinker can be any material that can be used in the composition of a hydraulic binder.

[0330] Mineral materials other than clinker suitable for the present invention include, 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 blast furnace slags (granulated or pelletized), 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.

[0331] In particular, the mineral material other than clinker is chosen from calcium sulfates and mineral additions, more particularly from calcium sulfates, calcined clays, limestones, natural or artificial pozzolans, fly ash and blast furnace slags, even more particularly from calcium sulfates, calcined clays, limestones, natural or artificial pozzolans, blast furnace slags, and any mixture thereof, advantageously from calcium sulfates, calcined clays, limestones, blast furnace slags, and any mixture thereof.

[0332] The hydraulic binder composition may in particular be as described in patent applications EP4330206A1, EP4330208A1, W02024023065A1 or W02024023066A1.

[0333] The expressions "from ... to ...", "between ... and ...", "ranging from ... to ...", "varies from ... to ...", and "less than ..." should be understood inclusive of limits, unless otherwise specified.

[0334] The invention will become clearer upon reading the following examples, which are not exhaustive.

[0335] EXAMPLE

[0336] EXAMPLE 1:

[0337] Evaluation of the performance of the adjuvant composition on a low-carbon hydraulic composition, with a specific ternary binder:

[0338] [Table 1]

[0339] The detailed composition of the ternary binder is as follows:

[0340] [Table 2] 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):

[0341] - 25.9% polymer A: with a = 49, b = 45, c = 6 and z = 17,

[0342] - 10.8% polymer C: 82.3, b = 17.7 and z = 53,

[0343] - 42.5% polymer D: with n=6, m=35, R = H or CH3 and the molar ratio PO / OE = 10 / 31 ,

[0344] - 11.1% calcium nitrate,

[0345] - 0.8% antifoams, of which 50% are alkyldimethylamine type and 50% are ethoxylated fatty alcohols, and

[0346] - 0.3% biocide, (ethylendioxy) dimethanol type.

[0347] Various rheological agents are added to the hydraulic composition of Table 1 and inverted cone measurements were carried out according to the NF P18-462 (2023) standard with filling in one go, without application of blows distributed on the surface of concrete.

[0348] 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 15x15x15cm cubic specimens 3 after 24h humid curing (RH = 100%) in a mold in a room maintained at 20°C.

[0349] Determination of the dosage of rheological agent: 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.

[0350] 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):

[0351] [Table 3] It has been observed that the use of a high molecular weight polycarboxylate reduces spreading, and this reduction is dependent on the dosage of the rheological agent. A dosage of 0.032% high molecular weight polycarboxylate thus reduces the spreading of the paste in the adjuvanted hydraulic composition by 38%. Similarly, the use of diutan gum or methyl hydroxyethyl cellulose reduces spreading, and this reduction is dependent on their dosage. These different rheological agents were introduced into the hydraulic composition in Table 1 at various dosages. The dosages indicated for rheological agent correspond to the dosages relative to the total mass of ternary binder.

[0352] The results are summarized in the following table: [Table 4]

[0353] : comparison

[0354] 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

[0355] It was observed that the use of a high molar mass polycarboxylate (Test B) reduced the flow time in the inverted cone by half compared to the reference concrete (Test A). The addition of Diutan gum or Methyl hydroxyethyl cellulose also resulted in this reduction of the flow time in the inverted cone.

[0356] This result is surprising because the rheological agent alone drastically increases the viscosity of the hydraulic composition, making it impossible for the concrete to flow through the cone (test G). The rheological agent and superplasticizers therefore act synergistically to improve the viscosity of the hydraulic composition over two hours of workability.

[0357] The addition of rheological agents has no impact on the compressive strengths measured at 24h and 20°C.

[0358] EXAMPLE 2:

[0359] Evaluation of the performance of the adjuvant composition on two low-carbon hydraulic compositions, with a specific ternary binder, differing from the composition in Table 1 by the W / C ratio and the specific ternary binder content:

[0360] [Table 5]

[0361] The details of the composition of the specific ternary binder are presented in Table 2.

[0362] 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):

[0363] - 24.9% polymer A: with a = 49, b = 45, c = 6 and z = 17,

[0364] - 31.9% polymer D: with n=6, m=35, R = H or CH3 and the molar ratio PO / OE = 10 / 31 ,

[0365] - 11.9% polymer E: with a = 43, b' = 16, b” = 41, z' = 53 and z” = 8. - 8.7% calcium nitrate,

[0366] - 0.7% antifoams, of which 50% are alkyldimethylamine type and 50% are ethoxylated fatty alcohols, and

[0367] - 0.35% biocide, (ethylendioxy) dimethanol type.

[0368] 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 the NF P18-462 (2023) standard with one-step filling, without application of blows distributed on the concrete surface.

[0369] The subsidence measurement was carried out according to the standard NF EN 12350-2 (2019).

[0370] Determination of the rheological agent dosage:

[0371] 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.

[0372] 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):

[0373] [Table 6] 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 necessary to achieve a 33% reduction in the spread of the paste of hydraulic composition no. 3.

[0374] The dosages indicated for rheological agent correspond to the dosages relative to the total mass of ternary binder.

[0375] The results are summarized in the following table:

[0376] [Table 7] * : comparison

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 polyalkyl polycarboxylates, 25% to 45% by mass of at least one water-reducing or high water-reducing adjuvant selected from polyalkyl 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 glycol and polyethylene glycol monomethyl ether, - latex, - polyacrylamides, - polyvinyl alcohols, - clays, - sodium alginates, and - any one of their mixtures.

3. Adjuvant composition according to claim 1 or 2, wherein 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, 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" represents each independently H + or a cation of valence 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 -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 - “R1” represents a C1-C20 alkyl group, a cycloalkyl group, an alkylaryl group, or -[Alkyl-O] z -R6, in which the "Alkyl" of each unit [Alkyl-O] independently represents a linear or branched alkylene comprising 2 to 4 carbon atoms, and "R6" represents H, a C1-C20 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 units (I) in the polymer, - "b" is a number ranging from 0.05 to 0.95, "b" being the mole fraction of formula units (II) in the polymer, - “L” represents a bonding group to the main chain of the polymer, and is specifically chosen from a direct bond, an oxygen atom, an -NR12- ​​group, R12 being a hydrogen or an alkyl group in C1 to C6, and an alkylene group in C2-C6, of 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 C1 to C20 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, - "R10" each independently represents a monovalent group, in particular chosen from a hydrogen, an alkyl group in C1 to C6, 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 an alkyl in C1 to C3, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation; - "R11" is a monovalent group, in particular chosen from a hydrogen atom, a hydroxyl group and an alkyl group in C1 to C10, preferably "R11" 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.

5. 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 either a hydrogen or a methyl group, - X = O, - R1 = -[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" group -[Alkyl-O] z - represent -CH2-CH2- , or even all the "Alkyl" of the -[Alkyl-O] group z - represent -CH2-CH2-, and / or - "z" represents an integer from 5 to 200, specifically 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 ranging from 0.10 to 0.80, preferably "b" is a number ranging from 0.15 to 0.60, - n = 0, - L is an oxygen atom or an -NR12- ​​group, advantageously L is an oxygen atom, - "R10" each independently represents a hydrogen, a C1-C6 alkyl group, or "R10" is a cation, in particular an alkali, alkaline earth or ammonium cation, preferably R10 is a hydrogen, - “R11” is a hydroxyl group, and - "c" is a number ranging 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. Adjuvant composition according to any one of the preceding claims, wherein the polyalkoxylated phosphonate polymers are of the following formula (IV): in which: - "R5" is a hydrogen atom or a monovalent hydrocarbon group comprising 1 to 18 carbon atoms and possibly one or more heteroatoms; - the "Ri" 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; - “Q” is a hydrocarbon group comprising 2 to 18 carbon atoms and possibly one or more heteroatoms; - "A" is an alkylene group consisting of 1 to 5 carbon atoms; - The "Rj" values ​​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 capable of bearing [R5-O(Ri-O)] groups m], R5 and Ri having the aforementioned meanings, - "m" is a number greater than or equal to 0, - "r" is the number of groups [R5-O(Ri-O) m supported by all the RJs, - "q" is the number of groups [R5-O(Ri-O) m carried 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 adjuvant or high water reducer selected from polyalkoxylated polycarboxylates and the total mass content of water-reducing adjuvant or high water reducer selected from 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.

Images