FLUIDIFYING COMPOUNDS FOR HYDRAULIC COMPOSITIONS

The subject of the present invention is new plasticizing compounds, intended in particular to be used in hydraulic compositions.

Hydraulic compositions are compositions comprising a hydraulic binder. A hydraulic binder is a binder that forms and hardens by chemical reaction with water. Mention may be made, as hydraulic binders, of compositions of sulphates and/or aluminates of calcium, lime and cement. Mortars and concretes, in particular precast concretes and ready-mixed concretes, are of particular importance. These materials may be intended in particular for building, civil engineering works or the manufacture of concrete parts.

It is known to add thinners (also called plasticizers or superplasticizers) to hydraulic binders, which make it possible to thin the hydraulic composition and thus reduce the water content of the hydraulic binder paste. Thus, the hydraulic binder paste has, after hardening, a denser structure. This results in a higher mechanical resistance.

Polyoxyalkylene polycarboxylates (PCPs) are known in particular, which are particularly effective for thinning hydraulic compositions and also called superplasticizers.

Other polymeric superplasticizers for the fluidification of concrete mortars have been developed, such as single-chain poly(ethylene oxide) bis phosphonates described in application FR 2 696 736, and marketed by the company CHRYSO under the name CHRYSO ® Fluid Optima 100. Application FR 2 925484 from the company LAFARGE SA also describes a type of polymeric superplasticizers for the fluidification of concrete mortars consisting of ester derivatives of gallic acid.

However, these superplasticizers exhibit limited water reduction properties and robustness to clays and alkali sulfates in solution. In addition, it should be noted that the chemical stability in a very strongly alkaline medium of concrete is very limited in the case of the structures described in application FR 2 925484.

There is therefore to date a need to have more effective thinning compounds.

The object of the present invention is therefore to provide novel compounds which perform particularly well as thinners in hydraulic compositions.

Thus, the present invention relates to a compound of formula (I) below:

in which :

• M is chosen from the group consisting of H, alkali metals and alkaline earth metals and groups + HNRR', R and R' being chosen independently of one another from H, (Ci-C3)alkyls, linear or branched, and C1-C3 alcohols, linear or branched;

• Ri is chosen from the group consisting of H, and (Ci-C4)alkyl groups, linear or branched, when A corresponds to formula (1) below, or, when A corresponds to formula (2) or (3) below, R1 is selected from the group consisting of H and (Ci-C4)alkyl groups, linear or branched;

• R2 is chosen from the group consisting of H, OM, M being as defined above and (Ci-C4)alkyl groups, linear or branched;

• A represents:

* a group
of the following formula (1):

(1 )

in which :

- n is an integer ranging from 1 to 40, preferably from 1 to 31;

- m is an integer ranging from 1 to 40, preferably from 1 to 31; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and (Ci-C 6 )alkyl groups, linear or branched;

. -C(=O)-NH- groups; and

. -C(R 5 )=N- groups, R 5 being H or Me, preferably H;

a group A 2 of the following formula (2):

in which :

- n is an integer ranging from 1 to 40, preferably from 1 to 31;

- m is an integer ranging from 1 to 40, preferably from 1 to 31;

- r is 0 or an integer ranging from 1 to 6; and

- M, Ri and R2 are as defined above in formula (I);

a group A 3 of formula (3) below:

in which :

- n' is an integer ranging from 1 to 50, preferably from 1 to 39;

- the sum m'+p' varies from 1 to 6;

- m' is an integer ranging from 1 to 5;

- p' is an integer ranging from 1 to 5; and

- M, Ri and R2 are as defined above in formula (I);

- Z is as defined above in formula (1).

In the context of the present invention, the following terms mean:

- C t -C z where t and z can take the values ​​of 1 to 6, a carbon chain which can have from t to z carbon atoms, for example C1-C4 a carbon chain which can have from 1 to 4 carbon atoms ;

- an alkyl group: a hydrocarbon-based, saturated, linear or branched aliphatic group comprising, unless otherwise stated, from 1 to 6 carbon atoms. By way of examples, mention may be made of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl or pentyl groups.

By way of alkali metal, mention may be made, for example, of sodium, lithium or potassium. Mention may be made, as alkaline earth metals, of magnesium and calcium.

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

Preferably, in formulas (1) and (2) above, n is an integer ranging from 1 to 31 and m is an integer ranging from 1 to 31.

According to one embodiment, the compounds of the invention are compounds of formula (I) above in which A represents a group
of formula (1) and Ri is chosen from the group consisting of H,
and groups (Ci-C4 )alkyls, linear or branched.

According to one embodiment, the compounds of the invention correspond to the following formula (II):

in which :

- Ri is chosen from the group consisting of H and (Ci-C4)alkyl groups, or represents a group A ^ of formula (1) as defined above; and

- M and R 2 are as defined above in formula (I) and

- n and m are as defined above in formula (1).

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

According to one embodiment, in formula (II), R 2 is an OM group, M being as defined above.

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

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

According to one embodiment, in formula (II), Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

According to one embodiment, in formula (II), Z is chosen from the group consisting of -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and groups (Ci-Ce) alkyls, linear or branched.

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

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

According to one embodiment, the compounds of the invention correspond to formula (II), in which:

- R 2 is an OM group, M being as defined above;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

According to one embodiment, the compounds of the invention correspond to formula (II), in which:

- R 2 is an OM group, M being as defined above;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is selected from the group consisting of -CHR 3 -NH- groups, R 3 being selected from the group consisting of H, COOH and (Ci-C 6 )alkyl groups, linear or branched.

Preferably, the compounds of the invention correspond to formula (II) as defined above, in which R1 is H or represents a group
of formula (1) as defined above.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group A ^ of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups.

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

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

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

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

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

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

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group A ^ of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H and COOH; and

. -C(=O)-NH- groups.

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

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (II), in which:

- Ri is H or represents a group of formula (1) as defined above;

- R2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is selected from the group consisting of -CHR 3 -IMH- groups, R 3 being selected from the group consisting of H and COOH.

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

Among the compounds of formula (II) according to the present invention, mention may be made in particular of the compounds corresponding to one of the following formulas:

m and n being as defined above, and preferably n=19 and m=3 or n=31 and m=10.

Among the compounds of formula (II) according to the present invention, mention may be made in particular of the compounds corresponding to one of the following formulas:

m and n being as defined above, and preferably n=19 and m=3 or n=31 and m=10.

According to one embodiment, the compounds of the invention are compounds of formula (I) above in which A represents a group A 2 of formula (2) and Ri is chosen from the group consisting of H and groups (Ci- C4) alkyls, linear or branched.

According to one embodiment, the compounds of the invention correspond to the following formula (III):

in which :

- Ri is selected from the group consisting of H and (Ci-C4)alkyl groups; and

- M and R2 are as defined above for formula (I), and

- n, m and r are as defined above for formula (2).

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

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

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

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

According to one embodiment, in formula (III), Ri is H.

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

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

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

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

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

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

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

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

According to one embodiment, the compounds of the invention are compounds of formula (I) above in which A represents a group A 3 of formula (3) and Ri is chosen from the group consisting of H and groups (Ci- C4) alkyls, linear or branched.

According to one embodiment, the compounds of the invention correspond to the following formula (IV):

in which :

- Ri is selected from the group consisting of H and (Ci-C4)alkyl groups; and

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

- n′, m′ and p′ are as defined above for formula (3).

Preferably, in formula (IV), n' is an integer ranging from 1 to 39.

According to one embodiment, in formula (IV), R 2 is an OM group, M being as defined above.

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

According to one embodiment, in formula (IV), Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

According to one embodiment, in formula (IV), Z is chosen from the group consisting of -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and groups (Ci-Ce) alkyls, linear or branched.

According to one embodiment, in formula (IV), Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H and COOH; and

. -C(=O)-NH- groups.

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

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- R2 is an OM group; and

- Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups; and

. -C(=O)-NH- groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- R2 is an OM group; and

- Z is chosen from the group consisting of -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups.

Preferably, in the aforementioned formula (IV), R1 is H.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- Ri is H;

- R2 is an OM group; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and (Ci-C 6 )alkyl groups, linear or branched; and

. -C(=O)-NH- groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- Ri is H;

- R2 is an OM group; and

- Z is chosen from the group consisting of -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and linear or branched (Ci-Ce)alkyl groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- Ri is H;

- R2 is an OM group; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H and COOH; and

. -C(=O)-NH- groups.

A preferred family of compounds of the invention is formed of compounds corresponding to the aforementioned formula (IV), in which:

- Ri is H;

- R2 is an OM group; and

- Z is selected from the group consisting of -CHR 3 -IMH- groups, R 3 being selected from the group consisting of H and COOH.

Among the compounds of formula (IV) according to the present invention, mention may be made in particular of the compounds corresponding to the following formula:

n', m' and p' being as defined above.

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

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

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

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

In the context of the present invention, the term “hydraulic binder” is understood to mean any compound having the property of hydrating in the presence of water and the hydration of which makes it possible to obtain a solid having mechanical characteristics, in particular a cement such as a Portland cement, aluminous cement, pozzolanic cement or else an anhydrous or semi-hydrated calcium sulphate. The hydraulic binder can be a cement according to standard EN197-1 (2001) and in particular a

Portland cement, mineral additions, in particular dairy, or a cement comprising mineral additions.

The expression “mineral additions” refers to slags (as defined in standard Ciment NF EN 197-1 (2012) paragraph 5.2.2), steelworks slags, pozzolanic materials (as defined in standard Ciment NF EN 197-1 (2012) paragraph 5.2.3), fly ash (as defined in standard Ciment NF EN 197-1 (2012) paragraph 5.2.4), calcined shales (as defined in standard Ciment NF EN 197-1 (2012) paragraph 5.2.5), limestone (as defined in the Cement standard NF EN 197-1 (2012) paragraph 5.2.6) or silica fumes (as defined in the Cement standard NF EN 197-1 (2012) paragraph 5.2.7) or their mixtures. Other additions, not currently recognized by the Cement standard NF EN 197-1 (2012), can also be used. These include metakaolins,

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

Among these plasticizers and / or superplasticizers, among those well known in the technical field, mention may be made, for example, of polyoxyalkylene polycarboxylates (PCP) or even the single-chain poly(ethylene oxide) bis phosphonates described in patent FR 2 696 736, and marketed by CHRYSO under the name of CHRYSO ® Fluid Optima 100.

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

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

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

The presence of phyllosilicate clay in a sand, preferably montmorillonites, even more preferably sodium montmorillonites, can strongly affect the workability of hydraulic binder compositions, in particular concrete compositions. Indeed, the sheet structure of clays promotes the absorption of water and the intercalation of the elements contained in the hydraulic binder compositions, such as for example superplasticizers. The proportioning of the quantity of clay is generally done by the methylene blue test (Standard NF EN 933-9).

These phenomena cause an increase in the viscosity of the hydraulic binder paste, and therefore a loss of workability. An overdose of thinner is then necessary to offset its consumption by the clays and maintain the desired performance. A plasticizer makes it possible to reduce the sensitivity to phyllosilicate clays of a hydraulic composition when the increase in its dosage to be iso-spreading is as low as possible, for example between 0% and 20%, when the rate of phyllosilicate clay varies .

The present invention also relates to the use of a compound as defined above, corresponding to the formula (I), or to one of the formulas (II), (III) or (IV) to reduce the sensitivity to alkaline sulphates in solution of a hydraulic composition.

Alkaline sulphates in solution are competitors for the adsorption of plasticizers on cement grains. The quantification of the rate of alkaline sulphates in solution is done by the method described in "Techniques and methods of the laboratories of bridges and roads, Test method ME48 - 4p - 1997". The thinning agent dosage is therefore dependent on the level of alkaline sulphates in solution and the higher this level, the higher the thinning agent dosage will be to obtain the same target performance. A plasticizer makes it possible to reduce the sensitivity to alkaline sulphates in solution of a hydraulic composition when the increase in its dosage to be iso-spreading is as low as possible, for example between 0% and 20%, when the level of sulphates alkalis in solution varies,

The invention also relates to the use of a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV), for the preparation of a hydraulic composition comprising:

- a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV),

- at least one hydraulic binder (for example a hydraulic binder, or two hydraulic binders for binary systems or three hydraulic binders for ternary systems),

- at least one aggregate, and

- some water.

The hydraulic compositions can in particular be concrete, mortar, a screed or a grout.

The hydraulic compositions are prepared conventionally by mixing the aforementioned constituents. The invention also relates to the method for preparing a hydraulic composition comprising the step of mixing:

- of a compound as defined above,

- at least one hydraulic binder,

- at least one aggregate, and

- water,

The components being added in any order.

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

Thus, according to another aspect, the invention relates to a fluidizer (or plasticizer) for hydraulic compositions comprising the compound as defined above in solution in a solvent, in particular in aqueous solution, preferably from 5% to 50% by weight of compound, in particular from 10% to 30% by weight, in particular of the order of 20% by weight relative to the total weight of the solution. The water of said aqueous solution can in particular be the pre-wetting water. “Pre-wetting water” means part of the total water, which is used to moisten the aggregates before mixing, making it possible to simulate the hygrometric state of the aggregates, which is often wet, in a concrete plant or on the site. Said aqueous solution comprising the compound may optionally comprise other additives, for example an anti-foaming agent, an anti-air-entrainment additive, a setting accelerator or retarder, a rheology modifier, another plasticizer (plasticizer or superplasticizer) and/or any other additive conventionally used in hydraulic compositions. In a preferred embodiment, said aqueous solution comprising the polymer comprises a plasticizer, in particular a superplasticizer, for

example a superplasticizer CFIRYSO® Fluid Premia 180 or CFIRYSO® Fluid Premia 196.

In the context of the present invention, the term “cement” is understood to mean a cement according to standard EN 197-1 (2001) and in particular a cement of the CEM I, CEM II, CEM III, CEM IV or CEM V type according to the Cement standard. NF EN 197-1 (2012). The cement may include mineral additions.

By "aggregates" is meant a set of mineral grains with an average diameter of between 0 and 125 mm. Depending on their diameter, aggregates are classified in one of the following six families: fillers, sand, sand, gravel, gravel and ballast (standard XP P 18-545). The most commonly used aggregates are:

- fillers, which have a diameter of less than 2 mm and for which at least 85% of the aggregates have a diameter of less than 1.25 mm and at least 70% of the aggregates have a diameter of less than 0.063 mm,

- sands with a diameter between 0 and 4 mm (in standard NF EN 13-242, the diameter can go up to 6 mm),

- bass with a diameter greater than 6.3 mm,

- gravel with a diameter between 2 and 63 mm.

The sands are therefore included in the definition of aggregate according to the invention.

The fillers can in particular be of limestone or dolomitic origin.

During the mixing step, other additives may be added, for example a mineral addition and/or additives, for example an anti-air-entrainment additive, an anti-foaming agent, a setting accelerator or retarder, a rheology modifier, another plasticizer (plasticizer or superplasticizer), in particular a superplasticizer, for example a superplasticizer CFIRYSO® Fluid Premia 180 or CHRYSO® Fluid Premia 196.

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

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

The present invention also relates to a hydraulic composition, chosen in particular from concretes, mortars, screeds and grouts, comprising:

- a compound as defined above, corresponding to formula (I), or to one of formulas (II), (III) or (IV),

- at least one hydraulic binder,

- at least one aggregate, and

- some water.

The hydraulic composition may further comprise the aforementioned additives.

EXAMPLES

PART 1 - SYNTHESIS OF COMPOUNDS

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

Jeffamine® M2070, M1000 and ED 600 were obtained from HUNTSMAN. The HPLC Chain:

- Thermo Scientific, UHPLC Ultimate 3000, equipped with Chromeleon 7.2 software

- Column: Thermo Scientific, Acclaim Carbonyl C18, Dimension: 4.6 x 150 mm, Diameter: 120 Â; 5 p.m.

- Detectors: DEDL: SEDEX LC LT ELCD; UV: UHPLC Ultimate 3000.

Example 1: Synthesis of a representative structure 1:

with n = 31 and m = 10

In a three-necked flask equipped with a condenser, the 37% formalin solution (1 equivalent; 0.03mol; 2.4g) is added drop by drop to a solution of Jeffamine® M2070 (1 equivalent; 0.03mol; 62 ,1g) in 60 ml of water. The reaction medium is stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is brought to 60° C. until the pyrogallol disappears (monitored by HPLC).

Example 2: Synthesis of a representative structure 2:

In a three-necked flask equipped with a condenser, the 37% formalin solution (2 equivalents; 0.06mol; 4.8g) is added drop by drop to a solution of Jeffamine® M1000 (2 equivalents; 0.06mol; 62 ,1g) in 100 ml of water. The reaction medium is stirred at ambient temperature for 1 h. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is brought to 60° C. until the pyrogallol disappears (monitored by HPLC).

Example 3: Synthesis of a representative structure 3:

with n = 19 and m = 3

In a three-necked flask equipped with a condenser, the 50% glyoxylic acid solution (1 equivalent; 0.03 mol; 4.42 g) is added drop by drop to a solution of Jeffamine® M2070 (1 equivalent; 0.03 mol ; 62.1 g) in 60 ml of water. The reaction medium is stirred at room temperature for 1 hour. Pyrogallol (1 equivalent; 0.03 mol; 3.78 g) is added to the reaction medium and the temperature is brought to 60° C. until the pyrogallol disappears (monitored by HPLC).

Example 4: Synthesis of a representative structure 4:

with n = 19 and m = 3

In a four-necked flask fitted with a Dean Stark and a condenser, Jeffamine® M1000 (1.1 equivalents; 0.194 mol; 193.98 g) and gallic acid (1 equivalent; 0.176 mol; 30 g) are introduced. The reaction medium is brought to 160° C. under vacuum and stirred until the pyrogallol disappears (monitored by HPLC).

Example 5: Synthesis of a representative structure 5:

with n = 9 and m + p = 3.6

In a four-necked flask equipped with a Dean Stark, a condenser, the Jeffamine®

ED-600 (1.1 equivalents; 0.194 mol; 116.39 g) as well as gallic acid (1 equivalent; 0.176 mol; 30 g) are introduced. The reaction medium is brought to 160° C. under vacuum and stirred until the pyrogallol disappears (monitored by HPLC).

PART 2 - APPLICATIONS

AFNOR standardized sand is introduced into the bowl of a PERRIER mixer. After mixing the sand for 30s at 140 rpm, the pre-wetting water is introduced into the bowl in 15s. The volume of this water is one third of the total volume of effective water to be added. The mixing is continued for 15s and the pre-moistened sand is left to rest for 4 min 30. Then, the cement and the limestone filler (origin: ERBRAY) are added to the pre-moistened sand and the whole is mixed at 140 rpm for 1 min before introduction of the rest of the effective total water and all of the adjuvant over 30s. The mixer is stopped to scrape the edges of the bowl to have a homogeneous mortar then the mixing is resumed for 1 min at 280 rpm.

The initial water reduction and workability retention are obtained by measuring the diameter of the spread obtained in accordance with the following procedure:

A mold reproducing the Abrahams cone at a half scale is filled with the mortar. In order to obtain the spreading, this cone is raised at 90° from the plate by performing a quarter turn. The spread is measured at 5, 30, 60 and 90 minutes on two diameters at 90° to each other with a ruler. The measurement indicated is then the average of the two spreads with an uncertainty of ± 10mm.

The tests are carried out at 20°C.

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

The chemical compositions used in the application studies are explained below.

Table 1: Chemical composition of compositions

Example 6: Comparison with a reference without adjuvant

Table 2: Hydraulic composition

The results are collated in Table 3 below concerning the spread in mm as a function of the time in minutes.

As observed, the compounds according to the invention have a fluidizing power. Indeed, for an equal volume of water added, the initial spreading is doubled with the use of the two structures of examples 1 and 3.

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

Table 4: Hydraulic composition

The results are collated in table 5 below concerning the spread in mm as a function of the time in minutes.

As observed, the compounds of the invention have a fluidifying power greater than that of CHRYSO®Fluid Optima 100. Indeed, for an equal volume of water added, the commitments in active matter to reach the same initial spreading are lower than the Optima 100.

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

Table 6: Hydraulic composition

The results are collated in Table 7 below concerning the spread in mm as a function of the time in minutes.

As observed, the use of a compound according to the invention (example 1) in combination with CHRYSO®Fluid Optima 100, makes it possible to obtain a higher fluidifying power while preserving an interesting maintenance of workability. In fact, for an equal volume of water added, the target spreading is achieved with a lower active ingredient commitment for the mixture than for CHRYSO®Fluid Optima 100 alone.

Table 8 below summarizes the results of the mechanical properties. The measurements of the mechanical resistance to bending and compression are made according to standard NF EN 196-1.

A strong increase in the resistances to bending (Rf) and to compression (Rc) is also observed after 24 hours, which is a desired performance in the field of application.

Example 9: Study of the robustness to alkalines

Table 9: Hydraulic composition

As observed, the use of a compound according to the invention makes it possible to obtain a robustness to the level of alkaline sulphates in solution of the fluidifying power, unlike the reference CHRYSO®Fluid Optima 100. Indeed, for an equal volume of water added , the dosage of CHRYSO®Fluid Optima 100 increases by 50% to obtain the same initial spread when the level of soluble alkaline increases while it remains identical for the compound of the invention.

A strong increase in the flexural and compressive strengths is also observed after 24 hours, which is a desired performance in the field of application.

Example 10: Comparative example with respect to the compounds of

WO 2009/112647

The compound of formula below was prepared:

In a three-necked flask fitted with a condenser, MPEG 500 (1.1 equivalent, 0.13 mol, 60.0g), gallic acid (1 equivalent, 0.12 mol, 21.2g) and acid paratoluene sulfonic (3.0 g) are added and heated to 130° C. under vacuum until the gallic acid has disappeared (monitored by HPLC).

Stability study at pH = 13

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

According to the chromatograms obtained, there is no change in the peak corresponding to the compound of Example 1 under the study conditions, whereas a strong reduction in the peak corresponding to the compound of Example 10 ( comparative). These peaks being representative of the molecule concentration in the medium, the instability of the structure according to application WO 2009/112647 is demonstrated in comparison with the structures according to the invention.

CLAIMS

1. Compound of formula (I) below:

in which :

• M is chosen from the group consisting of H, alkali metals and alkaline earth metals and groups + HNRR', R and R' being chosen independently of one another from H, (Ci-C3)alkyls, linear or branched, and C1-C3 alcohols, linear or branched;

• Ri is chosen from the group consisting of H,
and (Ci-C4)alkyl groups, linear or branched, when A corresponds to formula (1) below, or, when A corresponds to formula (2) or (3) below, R1 is selected from the group consisting of H and (Ci-C4)alkyl groups, linear or branched;

• R2 is chosen from the group consisting of H, OM, M being as defined above and (Ci-C4)alkyl groups, linear or branched;

• A represents:

* a group of the following formula (1):

in which :

- n is an integer ranging from 1 to 40, preferably from 1 to 31;

- m is an integer ranging from 1 to 40, preferably from 1 to 31; and

- Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being chosen from the group consisting of H, COOH and (Ci-C 6 )alkyl groups, linear or branched;

. -C(=O)-NH- groups; and

. -C(R 5 )=N- groups, R 5 being H or Me;

* a group A 2 of the following formula (2):

in which :

- n is an integer ranging from 1 to 40, preferably from 1 to 31;

- m is an integer ranging from 1 to 40, preferably from 1 to 31;

- r is 0 or an integer ranging from 1 to 6; and

- M, Ri and R 2 are as defined above in formula (I);

a group A 3 of formula (3) below:

in which :

- n' is an integer ranging from 1 to 50, preferably from 1 to 39;

- the sum m'+p' varies from 1 to 6;

- m' is an integer ranging from 1 to 5;

- p' is an integer ranging from 1 to 5; and

- M, Ri and R 2 are as defined above in formula (I);

- Z is as defined above in formula (1).

2. Compound according to claim 1, corresponding to the following formula (II):

in which :

- Ri is chosen from the group consisting of H and (Ci-C 4 )alkyl groups, or represents a group
of formula (1) as defined in claim 1; and

- M, R 2 , n, m are as defined in claim 1.

3. Compound of formula (II) according to claim 2, in which:

- R 2 is an OM group;

- n varies from 19 to 31;

- m varies from 3 to 10; and

- Z is chosen from the group consisting of:

. -CHR 3 -IMH- groups, R 3 being chosen from the group consisting of H, COOH and (Ci-C 6 )alkyl groups, linear or branched; and

. -C(=O)-NH- groups.

4. Compound of formula (II) according to claim 3, in which R is H or represents a group
of formula (1) as defined in claim 1.

5. Compound according to claim 1, corresponding to the following formula (III):

in which :

- Ri is selected from the group consisting of H and (Ci-C4)alkyl groups; and - M, R 2 , n, m and r are as defined in claim 1.

6. Compound of formula (III) according to claim 5, in which R 1 is H and R 2 is an OM group and r is 0 or varies from 1 to 3.

7. Compound according to claim 1, corresponding to the following formula (IV):

in which :

- Ri is selected from the group consisting of H and (Ci-C4)alkyl groups; and

- M, R 2 , n', m' and p' are as defined in claim 1.

8. Compound of formula (IV) according to claim 7, in which:

- Ri is H;

- R 2 is an OM group; and

- Z is chosen from the group consisting of:

. -CHR 3 -NH- groups, R 3 being selected from the group consisting of H,

COOH and (Ci-C 6 )alkyl groups, linear or branched; and

. -C(=O)-NH- groups.

9. Use of a compound according to any one of claims 1 to

8:

- as a chelating agent for positively charged ions,

- as a fluidizing agent for hydraulic compositions,

- for the admixture of hydraulic binders, alone or in combination with at least one plasticizer and/or superplasticizer,

- to reduce the sensitivity to phyllosilicate clays of a hydraulic composition, or

- to reduce the sensitivity to alkaline sulphates in solution of a hydraulic composition.

10. Hydraulic composition comprising:

- a compound according to any one of claims 1 to 8,

- at least one hydraulic binder,

- at least one aggregate, and

- some water.