FR2804424A1 - COMPOSITIONS BASED ON PHENOLIC DERIVATIVES AND THEIR USE AS ADJUVANTS OF MINERAL BINDERS - Google Patents

Abstract

The invention concerns a composition based on phenolic derivatives and their use as mineral binder additives, enabling to obtain mineral matrices, preferably of mortars and concrete mixtures, with improved properties. The invention also concerns a composition for binders, in the form of a powder or an aqueous suspension, comprising at least a phenolic derivative and at least a polymer. The invention further concerns methods for preparing those various compositions, and their uses in particular for making mortars and concrete mixtures.

Description

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COMPOSITIONS BASED ON PHENOLIC DERIVATIVES AND THEIR
USE AS ADJUVANTS OF MINERAL BINDERS
The subject of the present invention is a composition based on phenolic derivatives and their use as adjuvants for inorganic binders, making it possible to obtain mineral matrices, preferably mortars and concretes, with improved properties.

 It also relates to a composition for binders, in the form of powder or aqueous suspension, comprising at least one phenolic derivative additive and at least one amorphous silica.

 It also relates to a binder composition, in the form of a powder or aqueous suspension, comprising at least one phenolic derivative and at least one latex.

 The invention also relates to the processes for preparing these various compositions, and their uses in the manufacture of mortars and concretes in particular.

 Mortars and concretes are known to be prepared by mixing mineral binders, preferably cement, with water, and aggregates, such as sand and gravel.

 Although the specialist is accustomed to describe more specifically concrete, a composition in which the mineral filler is based on relatively large aggregates (of the order of 5 to 30 mm), and mortar a composition in which the mineral filler is based on finer aggregates, the term "concrete" will be used interchangeably in the present description to designate all types of compositions, regardless of the particle size, to simplify the presentation.

 Still with the aim of simplifying the disclosure, in the context of the present invention, the term "concrete" will refer, by extension, to cementitious matrices which are compositions free from sand and aggregates, and containing cement and, possibly, filler-type fillers (calcium carbonate, fly ash, slag, etc.).

 By extension, it also applies to adhesive mortars, smoothing compounds, patching compounds, repair mortars, self-leveling mortars, etc.

 The freshly prepared concrete, which will be hardened once in place, must remain stable until it is used.

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 This raises the problem of handling, in terms of maintaining the proper fluidity.

 This problem arises all the more often as concrete, which can of course be manufactured as and when needed at the point of use, is more and more frequently manufactured in a power station and then brought to the place of production. use. It is important then that the concrete has a suitable setting time, and keeps during the travel time, its stability and all its properties.

 Among the various properties, the fluidity which conditions the ease of implementation of the concrete, is an essential property.

 In order to obtain these fluidity properties, superplasticizing additives are generally added to the concrete, such as naphthalene sulphonate condensates, melamine sulphonate, of alkali and alkaline earth metal polycarboxylate type; polyacrylates of alkali and alkaline earth metals; alkylene polyoxides optionally grafted with a complexing group of calcium or their derivatives, optionally in combination with an aminoalkylene phosphonate; derivatives of polymers or copolymers based on acrylic or methacrylic acid, and terpolymers of acrylic or methacrylic acid or their salts.

 Another important property is the cohesion of the concrete. By "cohesion of concrete", one understands, among other things, its pumpability when it is about the fluid concrete, its plasticity when one looks for an easier implementation and a better aspect of surface, or its rebound when it is shotcrete.

 In order to preserve and / or improve the stability and the properties especially of fluidity and cohesion, concrete is usually incorporated into suitable additives. However, it is not uncommon for the additives, when added separately from each other and / or successively, to provide, in addition to the positive effect for which they are employed, a deleterious effect on other properties. .

 Thus, an agent improving the fluidity of the concrete, at high levels sometimes necessary to achieve the desired result, can very significantly degrade the cohesion of the concrete, and for example, have a negative effect on the pumpability (case of fluid concretes, for example ).

 Furthermore, it can also, at high doses, cause large amounts of air, which results in a degradation of the mechanical properties, and induce setting delays, which immobilizes the forms for long periods, thus limiting the progress of the sites.

 It has now been found, and this is the object of the present invention, that the addition of an effective amount of a phenolic derivative in a

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 cement matrix, preferably concrete, allowed to obtain advantageous properties.

 Thus, it has been demonstrated that the addition of a small amount of phenol derivative, preferably less than 0.5% relative to the weight of cement, made it possible to fluidize the concrete compositions without causing air, allowing to obtain concrete compositions both dense and fluid, which is not the case with the aforementioned superplasticizers, which cause air.

 In addition, the presence of the phenol derivative makes it possible to obtain, in an unexpected manner, concretes which have high mechanical characteristics at the young ages (tensile strengths by flexion and in simple compression), contrary to the common superplasticizers, which retard the acquisition of mechanical performance at young ages.

 In addition, it has been found that by advantageously combining a phenolic derivative adjuvant and an amorphous silica, preferably in the form of an aqueous suspension, the finished concrete is imparted with an improvement in cohesion, in particular by increasing the pumpability and the plasticity when said composition was incorporated in a fluid concrete, or reducing the rebound, when it was introduced in shotcrete.

 Another object of the invention therefore resides in an aqueous suspension of amorphous silica, characterized in that it comprises at least one amorphous silica and at least one phenolic derivative.

 The invention also relates to the processes for preparing this aqueous suspension and its use in cementitious matrices, concretes or mortars, in particular to improve their fluidity and cohesion, their mechanical properties at young ages, at 28 days, and at term .

 The essential constituent involved in the cementitious compositions of the invention is a phenol derivative.

 By "phenolic derivative" is meant any aromatic compound, preferably benzene bearing at least one hydroxyl group in free or functionalized form and carrying at least one other group comprising an oxygen atom and / or nitrogen and or sulfur: said group may be carried by the aromatic ring or be part of the functional group attached to the oxygen atom.

 The phenolic derivatives used preferentially, more particularly correspond to formula (I):

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OY1 O<X,)n dans ladite formule (1) : - Y1 représente : . un atome d'hydrogène, . un groupe alkyle linéaire ou ramifié ayant de 1 à 12 atomes de carbone, de préférence, de 1 à 4 atomes de carbone, . un groupe R qui peut être un groupe alkyle linéaire ou ramifié ayant de 1 à 12 atomes de carbone ou un groupe alcényle ou alcynyle ayant de 2 à 12 atomes de carbone porteur d'un groupe ionisable G sous forme acide ou safiée tel qu'un groupe carboxylique, carboxylate, sulfonique, sulfonate, hémisulfurique, sulfate, phosphonique, phosphonate, hémiphosphorique, phosphate sous forme acide ou salifié, . un groupe de formule (F) :

- R, R2 #CH-CH O H J rn (F) dans laquelle les groupes R1 et
R2, identiques ou différents, représentent un atome d'hydrogène, un groupe méthyle ou éthyle : lorsque l'un des groupes R1 ou R2 est un groupe méthyle ou éthyle, l'autre groupe R1 ou R2 est alors un atome d'hydrogène et m est un nombre compris entre 1 et 50.

OY1 O <X, n in said formula (1): Y1 represents: a hydrogen atom, a linear or branched alkyl group having from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms, an R group which may be a linear or branched alkyl group having 1 to 12 carbon atoms or an alkenyl or alkynyl group having 2 to 12 carbon atoms bearing an ionizable group G in acid or safed form such as a carboxylic, carboxylate, sulphonic, sulphonate, hemisulfuric, sulphate, phosphonic, phosphonate, hemiphosphoric, phosphate group in acid or salt form,. a group of formula (F):

- R, R2 # CH-CH OHJ rn (F) in which the groups R1 and
R2, identical or different, represent a hydrogen atom, a methyl or ethyl group: when one of the groups R1 or R2 is a methyl or ethyl group, the other group R1 or R2 is then a hydrogen atom and m is a number from 1 to 50.

X1 represents: a group -O-Y2, Y2, identical to or different from Y1, having the same meaning, a linear or branched alkyl group having 1 to 18 carbon atoms, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, dodecyl, hexadecyl, octadecyl; . a linear or branched alkenyl group having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl, a linear or branched alkoxy group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, an alkenyloxy group, preferably an allyloxy group or a phenoxy group,

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 . an acyl group of formula R3-CO- in which R3 represents a linear or branched alkyl group having from 1 to 17 carbon atoms, preferably acetyl, lauroyl, palmitoyl, stearoyl, a group = 0,. a -CHOH-COOH group, a group of formula: -R4-OH-R4-COOR5 -R4-COOM-R4-CHO-R4-NO2-R4-NH2-R4-CO-NH2-R4-NH-CH2-CH2-OH-R4-N- [CH2-CH2-OH] 2 in said formulas, R4 represents a valency bond or a linear or branched, saturated or unsaturated divalent hydrocarbon group having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene isopropylene, isopropylidene; the groups R5 which are identical or different represent a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms, a metal cation, preferably an alkaline cation or an ammonium group, a group -S03M in which M represents a hydrogen atom or a metal cation, preferably an alkaline cation or an ammonium group, - two X1 groups on two vicinal carbon atoms or two OY1 and X1 groups on two atoms vicinal carbon may be linked by a methylenedioxy or ethylenedioxy bridge, - if n is 0, Y1 is R, - if Y1 is hydrogen, n is at least 1.

 n is a number ranging from 0 to 5, preferably equal to 1, 2 or 3.

 Intervenes according to the invention, phenol derivatives corresponding to formula (I) wherein the Y1 group represents a hydrogen atom. In this case, X1 represents more particularly a formyl group or a carboxylic group.

 When the phenol derivatives correspond to the formula (I) in which the hydroxyl group is converted into an oxyalkylenated group as represented by

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 formula (F), the group R2 preferably represents a hydrogen atom or a methyl group and the group R1 represents a hydrogen atom.

 The number of oxyalkylenated units may vary widely from 1 to 50, but is preferably from 1 to 20.

 The invention also relates to phenolic derivatives comprising several types of oxyalkylenated units, in particular oxyethylenated units and oxypropylene units: said units are distributed in a statistical or sequential manner.

 They are represented more preferably, by the formula (I) in which: -p + q = m, -p + q1, 15-p is between 0 and 5, - q is between 0 and 10.

 The invention relates to oxyalkylenated phenol derivatives corresponding to formula (1), in which X1 represents one or two sulphonic groups in salified form, preferably in the form of an alkali metal, (preferentially sodium or potassium). , alkaline earth or an ammonium group.

 Such compounds that can be used according to the invention are described in applications FR 98/04918 and 98/04919.

 Phenolic derivatives according to the invention having the formula (1), in which the group Y1 represents a functional group represented by the group R. The invention does not exclude that the group R as defined is interrupted by a heteroatom, oxygen or nitrogen, or a functional group such as carbonyl, carboxy, amino, amido, sulfone, etc.

 It should be noted that when n is equal to 0, X1 represents a group of type R 30 comprising an ionizable group.

 As more specific examples of phenol derivatives that are quite suitable for the implementation of the invention, mention may be made in particular of the following families of compounds: diphenol compounds, vanillin precursors and derivatives, salicylates, and phenolic nitrogen compounds.

Examples of phenolic derivatives which can be used as adjuvants for binders, preferably mortars and concretes, are given below.

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phenoxyacetic acid.

the diphenolic compounds, pyrocatechol,. resorcinol,. 1,4-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, Sodium 4,5-dihydroxybenzene-1,3-disulfonate, Sodium 2,5-dihydroxybenzene-1,4-disulfonate, Sodium 4,5-bis (2-hydroxyethoxy) benzene-1,3-disulfonate,. Sodium 4,5-bis (2-hydroxy-1-propoxy) benzene-1,3-disulfonate, Sodium 4,6-bis (2-hydroxyethoxy) benzene-1,3-disulfonate,. 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzoquinone,. 2,6-dinitro-4-methoxyphenol,. 4-amino-1,2-dihydroxybenzene, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic acid, 2-hydroxyphenoxyacetic acid.

 . methylenedioxybenzene, - nitrogenous phenolic compounds.

 . 2-aminophenol, 3-aminophenol,. 2-amino-1- (2-hydroxyethoxy) benzene, 3-amino-1- (2-hydroxyethoxy) benzene, 2-amino-o-cresol, 3-amino-o-cresol, 6-amino-m-cresol - vanillin precursors,. the guetol,. vanillomandelic acid,. orthovanillomandelic acid,. the mandelic acid of catechol,

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 . methylenedioxybenzenemandelic acid,. p.trifluoromethylmandelic acid,. 2,6-difluoromandelic acid, vanillins and derivatives, vanillin,. ethylvanillin,. orthovanillin,. isovanillin,. the veratric aldehyde,. veratric acid,. vanillic acid,. orthovanillic acid,. isovanillic acid,. vanillin and its isomers in the form of sulphite, - salicylates,. salicylic aldehyde,. salicylic acid,. 5-nitrosalicylic acid,. 5-aminosalicylic acid,. the sodium salt of 5-sulfosalicylic acid, 5-chlorosalicylic acid,. 5-methylsalicylic acid,. O-acetylsalicylic acid,. salicylamide,. 2-hydroxyethoxy-4-hydroxybenzoic acid, 2-hydroxyethoxy-4-sodiooxysulfonylbenzoic acid.

 The phenol derivative is used in any binder composition in an amount which may be from 0.05 to 3%; preferably from 0.1 to 0.3% by weight of the binder expressed as solids.

 It may be introduced either at the level of the manufacture of the binder, preferably a cement, for example, during the grinding of the clinker, or further downstream during the manufacture of the mineral matrix, preferably a mortar or concrete.

 The process according to the present invention is applicable to all kinds of inorganic binders, including cements, hydraulic lime, fatty lime, artificial lime, cement mixes / hydraulic lime or lime, plaster, etc.

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 The process according to the invention applies with particular success to cements. The term "cement" refers to all combinations of (lime + silica + alumina) or (lime + magnesia + silica + alumina + iron oxide) commonly known as hydraulic cements. The preferred cements are Portland-type cements in which the clinker is at least 65% by weight; the possible additions, which are at most 35% by weight, may be fly ash from thermal power plants, pozzolans, blast furnace slag, fillers or mixtures of these products. These Portland cements still contain, in general, calcium sulphate, which is introduced in the form of gypsum CaSO4.2H2O, or anhydrite CaSO4.

 Special cements, such as masonry cements and masonry binders, can still be used.

 With regard to aggregates - sand, gravel or pebbles - their nature, grain size and proportions may vary over wide areas.

All mixtures of known types can be envisaged.

 The making of mortars and concretes is carried out according to known and standardized methods. It should be noted that in practice, the adjuvant of the invention can be introduced before mixing, in the hydraulic binder and aggregates, which can thus be premixed dry, or preferably be introduced into the mixing water. Said composition can also be introduced into the mortar or the fresh concrete, immediately before its use.

 If the phenolic derivative is in solid form, it is advantageously introduced by dry premixing with the other constituents of mortars and concretes.

 If the phenol derivative is in liquid form, it can be introduced into the mixing water, or else deposited on a support (silica or calcium carbonate, for example), in order to introduce it in solid form.

 According to a preferred embodiment of the invention, the phenolic derivative is associated with an amorphous silica, thus making it possible to improve the fluidity and homogeneity of the cement paste obtained.

 In the context of the present invention, the amorphous silica can in particular designate silica fumes, precipitated silicas, silica sols, pyrogenic silicas, silica compounds of natural or synthetic origin, smectites, silicates magnesium in general, and mixtures thereof.

 It is preferable to use a precipitated silica.

 By "precipitated silica" is meant here a silica obtained by precipitation from the reaction of an alkali metal silicate with an acid, in general

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 inorganic, at a suitable pH of the precipitation medium, in particular a basic, neutral or slightly acidic pH.

 The mode of preparation of the silica may be arbitrary (addition of acid to a silicate stockstock, simultaneous total or partial addition of acid or silicate to a stock of water or silicate solution, etc. ), and is chosen according to the type of silica that one wishes to obtain. At the end of the precipitation step, the step of separating the silica from the reaction medium is generally carried out according to any known means, filter press, or vacuum filter, for example. A filter cake is thus collected, which is washed if necessary. This cake may be, optionally after disintegration, dried by any known means, in particular by atomization, then optionally ground and / or agglomerated.

All of these protocols are described in detail in application EP 736 501, to which reference will be made.

 The amorphous silica is preferably chosen in the form of an aqueous suspension. Indeed, it is very interesting from an economic point of view to use such suspensions, because their use avoids the use of separate devices for the separate and / or successive introduction of silica and phenol derivatives of the invention.

 Furthermore, it has been noted that the addition of the phenol derivative in the aqueous silica suspension makes it possible to increase the stability of the silica suspension by virtue of its dispersing effect. Moreover, in a very advantageous manner, the presence of said phenolic derivative confers on the suspension a better resistance to bacterial attacks.

 The aqueous suspension involved in the invention advantageously has an amorphous silica content of between 1 and 60% by weight, preferably between 1 and 49%, and even more preferably between 3 and 35% by weight, relative to the total weight of suspension.

 As mentioned previously, it is preferred to use a precipitated silica. In the aqueous suspension, the precipitated silica consists of particles generally having a CTAB specific surface area of between 50 and 250 m 2 / g, and in particular between 100 and 240 m 2 / g. The CTAB surface is the external surface determined according to the standard NFT 45007 (November 1987).

 The suspension according to the invention advantageously contains a precipitated silica having good dispersibility and deagglomeration.

 It is thus possible to use a precipitated silica as described in EP-A-520 862 and EP-A-736 489.

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 The silica, in particular the precipitated silica, contained in the aqueous suspension, can be finely divided, especially following grinding (for example wet grinding) or ultrasonic deagglomeration.

 According to another embodiment of the invention, a silica sol is used.

Thus, the aqueous suspension is characterized in that it preferably comprises at least one aqueous silica sol and at least one superplasticizing agent chosen from alkali metal and alkaline earth polycarboxylates; polyacrylates of alkali and alkaline earth metals; alkylene polyoxides optionally grafted with a complexing group of calcium or their derivatives, optionally in combination with an aminoalkylene phosphonate; derivatives of polymers or copolymers based on acrylic or methacrylic acid; and terpolymers of acrylic or methacrylic acid or their salts.

 Aqueous silica sols are aqueous dispersions of colloidal silica, in which the silica is present in the form of spherical particles which are not crosslinked to each other and which carry hydroxyl groups on the surface. The physical and chemical properties of the silica sols, as well as their manufacturing process are described in Ullmans Encyclopedia of Technische Chemie, 4th edition, Volume 21, pages 456-458.

 When the amorphous silica suspensions are aqueous silica sols, said sols advantageously have a particle size of between 4 and 60 nm, and a BET specific surface area ranging from 45 to 700 m 2 / g.

 The BET surface area is determined according to the method of BRAUNEREMMET-TELLER described in "The Journal of the American Chemical Society", Vol. 60, page 309, February 1938, and corresponding to standard NFT 45007 (November 1987).

 Whether the amorphous silica is in the form of an aqueous or colloidal suspension, according to the process of the invention, it is associated with at least one phenolic derivative.

 The latter may be introduced during or at the end of the preparation of the aqueous suspension of silica. It should be noted that this term, used in the rest of the text, also covers silica floors.

 The amount of the phenolic derivative present in the aqueous suspension of silica, expressed in dry extracts, can represent from 0.5 to 5% of the total weight of the suspension, and preferably at least 1% of the total weight of the suspension.

 The present invention also relates to processes for preparing an aqueous suspension involving the phenolic type additive as defined according to the invention.

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 The aqueous suspension according to the invention can be prepared (especially on site) from a composition in the form of a powder comprising at least one amorphous silica in powder form, and at least one phenolic derivative in the form of powder according to a process consisting of mixing, with stirring (mechanical stirring in particular); it suffices to introduce this composition into the mixing water, and to mix the whole obtained.

 Said aqueous suspension may also be prepared, optionally according to a process consisting of mixing, with stirring (mechanical stirring in particular), at least one amorphous silica corresponding to the above definition, in the form of a powder, with an aqueous solution of the phenolic derivative, and possibly water.

 Said aqueous suspension may also be prepared optionally according to a process consisting of mixing, with stirring (mechanical stirring in particular), an aqueous silica suspension of at least one amorphous silica, with at least one phenolic derivative in the form of a powder, and optionally of the water.

 The aqueous suspension may finally be prepared optionally according to a process consisting of mixing, with stirring (mechanical stirring in particular), an aqueous suspension of at least one amorphous silica, with an aqueous solution of at least one phenolic derivative, and optionally with 'water.

In particular, this process consists in adding, with mechanical stirring, an aqueous solution of at least one phenolic derivative in an aqueous suspension of at least one precipitated silica, and optionally water, and further stirring the mixture and got. The temperature at which the addition is carried out is chosen according to the nature of the phenol derivative, so as to avoid the degradation of the latter.

 In order to prepare a concrete having a better fluidity and an improved cohesion, the aqueous suspension according to the invention can be added in a proportion of 0.1 to 15% by weight, and preferably 2.5 to 5%, relative to the weight of cement used to prepare the concrete.

 The invention finds particular application in so-called specialty concretes, which must have particular properties of rheology in the fresh state, of appearance in the cured state, of long-term mechanical strength (in particular in flexural tensile strength, and in compression), and among others, fluidity during implementation.

 Examples include fluid concretes, pumpable concretes, concretes for the manufacture of pavements (cement-based screeds, fluid mortars for screeds), submarine concretes which must be easily pumpable and

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 injectables, concrete facing, concretes for industrial floors, smoothing and smoothing coatings for surfaces, in particular for floors, concretes for spraying, and light concretes, concrete or grout for injection, soil consolidation, and cementing the oil wells, all these concretes having their properties improved thanks to the invention.

 More particularly, in the case of fluid concretes, not only the high fluidity, which is often desirable, but also an improvement in pumpability is achieved thanks to the invention, which makes it easier to set up.

 In the case of concretes to be sprayed, the invention makes it possible to obtain, in addition to the high fluidity, a considerable reduction in the rebound of the shotcrete.

 The addition of the aqueous suspension of the invention can be done at the time of mixing the concrete, or possibly in the mixing water.

 The subject of the invention is also the use of an aqueous suspension, as described above, in a medium of the cement matrix, concrete or mortar type, as an agent improving the cohesion of said medium.

 According to another embodiment of the invention, at least one phenolic derivative is associated with a superplasticizer when its presence is required in the intended application.

 Indeed, the presence of the phenolic derivative makes it possible to minimize the secondary effects resulting from the implementation of a superplasticizer, namely the entrainment of the air which causes the decrease in compressive strength in the long term (28). days).

 It is thus possible according to the invention to reduce the amount of superplasticizer used which limits the risks of bleeding (rise of milt on the surface).

 Thus, the amount of superplasticizer can be less, namely 0.3 to 1% by weight of the cement.

 In the context of the present invention, it is possible to use as superplasticizers, any superplasticizer conventionally used in the field considered, but it will be ensured in its choice that there is no incompatibility with the derivative phenol, such as, for example, gelation or caking or a chemical reaction causing the loss of dispersant properties.

 More specific examples of superplasticizers include naphthalene sulphonate condensates, melamine sulphonate, alkali and alkaline earth metal polycarboxylates; the

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 polyacrylates of alkali and alkaline earth metals; alkylene polyoxides optionally grafted with a complexing group of calcium or their derivatives, optionally in combination with an aminoalkylene phosphonate; derivatives of polymers or copolymers based on acrylic or methacrylic acid, and terpolymers of acrylic or methacrylic acid or their salts.

 It is possible to use mixtures of superplasticizers.

 These superplasticizers are known and described in particular in the practice of cements and concrete Michel Vénuat (Edition of the Monitor of public works and building pp. 131-137 and concretes, bases and data for their formulation Jacques Baron and Jean-Pierre Ollivier pp 96 -120 / French School of Concrete.

 It is thus possible to prepare according to the invention compositions comprising both the phenolic derivative and the superplasticizer, in powder form or in liquid form.

 Thus, they may comprise: from 10 to 90% by weight of at least one phenolic derivative, from 10 to 90% by weight of at least one superplasticizer.

 In the case of a liquid composition, the aqueous suspension of phenolic derivative (s) and superplasticizer (s) has a concentration by weight of dry matter most often between 20 and 50%.

 As more specific examples of compositions in powder form, mention may be made of those resulting from the combination of MELMENT F10 # sold by C.I.A. FOSROC (melamine sulphonate condensate) and salicylic acid.

 The mixture of phenol derivative and superplasticizers, whether in the form of powder or liquid, is introduced into the cement in a proportion of 0.5 to 5% by weight.

 As regards the implementation of this mixture, it can be introduced when it is in powder form, with dry products, such as cements, aggregates and other adjuvants.

 When in the form of an aqueous suspension, it can be added in the mixing water or in the wet paste obtained at the time of manufacture of the mortar.

 The mixture can be used to make a concrete slab, a smoothing compound or a mortar or self-leveling fluid concrete.

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 Its implementation makes it possible to improve the rheology of the paste (its fluidity) and to obtain improved mechanical properties of concrete or mortar obtained in the medium term (7 days) and in the long term (28 days).

 The present invention more specifically describes the phenolic derivative / silica or phenol derivative / phenolic resin / derivative or superplasticizer derivative, whether in solid or liquid form, but it also includes the ternary or quaternary phenolic derivative / silica and / or resin and / or or superplasticizer.

 The fields of application of the adjuvants of the invention are very wide.

 These include paving concrete, smoothing plasters, self-leveling mortars, tiling mortars, interior or exterior coatings, etc.

 The adjuvants according to the invention can be used advantageously in smoothing coatings. Generally these are binary mixtures of Portland cement and aluminous cement, or ternary mixtures including, in addition, calcium sulphate (eg hemihydrate, natural gypsum or synthetic gypsum) up to 10% .

 Thus, it has been found that it is possible, by using an adjuvant of the invention (for example 0.1 to 0.5% by weight of binder), to lower the content of aluminous cement with respect to the cement. Portland, while keeping the same open time, the same setting kinetics, and mechanical properties at least equivalent. More specifically, the addition of a small amount of phenol derivative makes it possible to pass, for example, a cementitious composition comprising by weight: - 70 to 75% of Portand Artificial cement, - 25 to 30% of aluminous cement, to a composition comprising: - 90 to 95% Artificial Portland cement, - 5 to 10% aluminous cement.

 The adjuvants according to the invention can be advantageously used in self-leveling fluid mortars.

 The term "self-leveling fluid mortar" is a mortar that is generally pumped to obtain, after application or casting on a horizontal surface, a screed that is free of surface irregularities and perfectly horizontal, without mechanical treatment of the surface. surface (such as in particular a smoothing) following the casting of said mortar.

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 The self-leveling fluid mortar comprises at least one inorganic binder, preferably a Portland cement (in particular CPA CEM 1 or CPJ CEM II) or aluminous cement, calcium sulfate, of natural or synthetic origin; aggregates, preferably siliceous or silico-calcareous sand, optionally a setting regulator, a fluidizer, and preferably at least one (co) polymer resin, and water called mixing water.

 It is thus possible to use an anhydrous calcium sulphate CaSO 4 (in particular anhydrite CaSO 4 of natural origin, or of synthetic origin, in the form of fluoro-, phospho-, sulpho- or titano-anhydrite), and / or a partially hydrated calcium sulphate, in particular α-hemihydrate CaSO4.1 / 2H20.

 The fluid mortar has, in general, a weight ratio of granules / inorganic binder of between 1 and 6, for example between about 1.2 and 2.0.

 The amount of water (called mixing water) present in the fluid mortar according to the invention is usually between 30 and 60%, for example between 40 and 50%, by weight relative to the weight of inorganic binder.

 The (co) polymer resin (i.e., a polymer or copolymer resin) used is of natural or, generally, synthetic origin.

 It can consist of a styrene-butadiene copolymer, a (co) polymer of vinyl ester (s), a (co) polymer of vinyl acetate; a (co) polymer of ethylene acetate.

 It is thus possible to use a polymer of vinyl acetate.

 It is also possible to use a copolymer of vinyl acetate and at least one vinyl ester of saturated monocarboxylic acids, branched or unbranched, having from 1 to 12 carbon atoms, such as propianate, pivalate or laurate. preferably, the versatate (trademark designating mixtures of branched acid esters having from 9 to 12 carbon atoms) of vinyl.

 The (co) polymer resin may also consist of a copolymer of a vinyl ester, in particular vinyl acetate, and of at least one unsaturated mono- or di-carboxylic acid ester having from 3 to 6 atoms. carbon and alkyl having 1 to 10 carbon atoms, such as acrylates, methacrylates, maleates, fumarates of methyl, ethyl, butyl, ethylhexyl.

 The (co) polymer resin can be used either in powder form or in dispersion in water (this is called latex).

 The resin content is between 5 and 60% by weight, preferably between 10 and 50% by weight, relative to the total weight of the suspension.

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 The amount by weight of (co) polymer resin in said mortar is advantageously between 0.5 and 6%, in particular between 1.5 and 3%, relative to the weight of inorganic binder.

 It can also contain a setting accelerator or a fluidifier.

 K 2 SO 4 potassium sulphate, lime, in particular slaked lime Ca (OH) 2, or, preferably, a mixture of potassium sulphate K 2 SO 4 and lime Ca (OH) 2 are advantageously used as setting accelerators. , or a retarding agent, for example lignosulphonates, starches, polysaccharides - such as Xanthan gums, Guar gums, acids and salts of hydroxy-carboxylic acids of low acidity, such as for example citric acid, tartaric acid, oxalic acid, etc.

 The total amount by weight of setting regulator (s) in said mortar is then generally between 0.1 and 5%, in particular between 0.5 and 2.5%, by weight, relative to the weight of inorganic binder. .

 Examples of plasticizers that may be mentioned include melamines, polymelamines, polynaphthalenes (especially sodium, calcium or potassium polynaphthalene sulfonate), polyacrylates (especially sodium, calcium or potassium polyacrylate), lignosulfonates, etc.

 The fluid mortar according to the invention may contain, in addition, at least one plasticizer, generally between 0.1 and 2.5%, in particular between 0.2 and 1.5%, by weight, relative to the weight of binder. mineral.

 Preferably, the fluid mortar according to the invention further comprises the phenolic derivative, anhydrite or a-hemihydrate, sand, a (co) polymer of vinyl acetate, a fluidizer, a regulator of setting, lime and water.

 According to the invention, the adjuvant according to the invention is used in the fluid mortar according to several embodiments, which can be chosen according to the physical form of the phenol derivative and the resin.

 The fluid mortar according to the invention is generally prepared by mixing the products used in its constitution (mixing operation); of introducing said products into the mixer may be arbitrary.

 In the case where the phenol derivative and the resin are in powder form, they can be intimately mixed dry separately and then introduced into the dry mixture of hydraulic binder, granulates and other additives.

 One thus obtains, and this constitutes another object of the invention, a usable composition (in particular on the site) for the preparation of a self-leveling fluid mortar, composition which has the same formulation (or constitution) as the fluid mortar, according to the invention, described above,

<Desc / Clms Page number 18>

 except that said composition does not include water; it suffices then to introduce this composition into the mixing water, and to knead the assembly obtained.

 It is also possible to prepare the same composition without water, with the exception of aggregates which are not introduced immediately, but during mixing.

 It is first possible to introduce the (co) polymer resin (and any setting and / or fluidizing regulators) into the water preferably, corresponding to the quantity of water required for the mixing leading to a latex, and then incorporated therein. the phenolic derivative. The hydraulic binder can then be introduced into the mixture obtained, and the mixture is then kneaded, then the aggregates are gradually added, and kneading is continued.

 The phenol derivative may be present in the latex suspension in an amount that may advantageously vary between 0.1 and 10% of the resin weight expressed as solids, and preferably between 1 and 5%.

 The phenol derivative can also be introduced upstream of the manufacture of the mortar. For example, it can be introduced during the preparation of the latex, or during the drying of the latex by any known means (eg spray tower), to obtain a powder.

 Thus, an additivated polymer powder with at least one phenolic derivative is obtained.

 The presence of the phenol derivative in the mortar according to the invention makes it possible to improve the rheology of the screed obtained from said mortar.

 Thus, the invention also relates to the use of a phenol derivative, as an additive for improving the mechanical strength in a screed obtained from a self-leveling fluid mortar comprising, in addition to said additive, at minus a mineral binder, aggregates and water.

 The screed obtained from the fluid mortar according to the invention is set up generally by pumping and applied, in particular by casting it on a horizontal surface.

 The adjuvants according to the invention can be advantageously used in adhesive mortars. These make it possible to bind together different materials, such as concretes, bricks, tiles, stones, etc. They are mainly used for laying tiles, and various tiles.

 Most often, these are cement mortars which comprise from 2 to 20% of a synthetic resin as mentioned above. They also contain other additives such as fillers and / or pigments; emulsifying agents of ionic or non-ionic nature, plasticizers (dibutyl phthalate, tricresyl phosphate); thickeners (carboxymethylcellulose, methylcellulose,

<Desc / Clms Page number 19>

 ethylcellulose, alkaline and alkaline earth alginates); anti-freeze agents; anti-foaming agents (silicone products, or dialkyl phosphate containing from 15 to 20 carbon atoms); anti-fungal agents, etc.

The phenol derivative can be introduced as a powder into the mixture of solid ingredients (cements and various fillers)
It can also be introduced, whether solid or liquid, into the mixing water, during application.

 It generally represents from 0.1 to 0.5% of the weight of the binder.

 It has been found that the presence of a phenolic derivative leads to an increase in viscosity, which makes it possible to lower the level of thickening agent, to reduce the sliding of the materials during bonding, and to improve the characteristics of the adhesion (resistance to tearing of the tiles, under different conditions of conservation). This adhesion results in a "cohesive" type break (rupture in the mass of the mortiercolle), during the tear test.

 The following examples illustrate the invention without, however, limiting its scope.

EXAMPLES
The examples relate to three main applications, namely paving concretes, adhesive mortars for tiles, and smoothing coatings.

Example 1
Tests on formulas of "Concrete paving"
The working formula is as follows: CPA CEM I 52.5 LAFARGE "St VIGOR" 350 kg / m3 Fly ash from Carling (SURSCHITES-CDF) 50 kg / m3 Sand 0/5 R 850 kg / m3 Gravel 5115 R 1061kg / m3 Water [E / C = 0.60] 210 liters
The adjuvants tested are as follows (the quantities are expressed in% of the weight of the cement): a) reference: GLENIUM 27 0.5% b) 0.1% TIRON c) 0.1% pyrocatechol d) 0.1 SALICYLIC ACID % e) 5-aminosalicylic acid 0.1%

<Desc / Clms Page number 20>

1 GLENIUM is a modified polycarboxylic ether of M. B.T. (S.K.W).

 2 TIRON is the disodium salt of 4,5-dihydroxy-1,3benzenedisulfonic acid.

 Pyrocatechol and 5-aminosalicylic acid are hereinafter referred to as "CATECHOL" and "5-A.S.A." respectively.

 All the ingredients were added in powder form (apart from GLENIUM 27, which is presented in liquid form), in fresh concrete (after introduction of the mixing water).

1. Effects on the rheology of concretes:
The rheology of the concretes studied was characterized through the FlowTest (shaking table tests, according to ASTM C 124 and AASHTO T 120 standards) and the Slump-Test (Abrams cone tests, according to NF standards). P.18-451 and ISO 4109).

 The results obtained are recorded in Table (1).

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Table (I) Rheological Characterization of Paving Concrete Formulations Containing Phenolic Derivatives.

<Tb>

Concrete <SEP> + 0.5% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1%
<tb> control <SEP> GLENIUM # <SEP> 27 <SEP> TURN <SEP> CATECHOL <SEP> ACID <SEP> 5-A. <SEP> SA
<Tb>

SALICYLIC
<tb> Density <SEP> fresh <SEP> po <SEP> 2.31 <SEP> 2.19 <SEP> 2.41 <SEP> 2.33 <SEP> 2.26 <SE> 2.30
<tb> Slump-test <SEP> 4.5 <SEP> 10 <SEP> 4 <SEP> 2 <SEP> 4.5 <SEP> 5
<tb> (cm)
<tb> Spreading <SEP> to <SEP> 0 <SEP> Strokes <SEP> 260 <SEP> 290 <SEP> 260 <SEP> 260 <SEP> 260 <SEP> 260
<tb> (mm)
<tb> Spreading <SEP> to <SEP> 5 <SEP> Strokes <SEP> 280 <SEP> 420 <SEP> 322 <SEP> 280 <SEP> 310 <SEP> 310
<tb> (mm)
<tb> Spreading <SEP> to <SEP> 10 <SEP> Strokes <SEP> 310 <SEP> 500 <SEP> 370 <SEP> 300 <SEP> 360 <SEP> 355
<tb> (mm)
<tb> Spreading <SEP> to <SEP> 15 <SEP> strokes <SEP> 350 <SEP> 540 <SEP> 420 <SEP> 330 <SEP> 410 <SEP> 410
<tb> (mm)
<Tb>

<Desc / Clms Page number 22>

It is observed that products of the type SALICYLIC ACID, 5-A.S.A. and TIRON lead to an improvement of the fluidity of the fresh dough.

 CATECHOL leads to a phenomenon of clamping of the paste, which can be linked to an acceleration of the setting phenomenon.

 GLENIUM 27 leads to the best rheological characteristics, but this seems partly due to an air entrainment phenomenon (see density values of fresh pasta).

2. Effect on mechanical strengths:
The strength tests were carried out on prismatic specimens measuring 7 × 7 × 28 cm 3 (standards NF, P 18-400, ASTM C31, AASHTO T23) demolded after 24 hours, and stored at 20 ° C. in water saturated with lime.

 The mechanical tests took place at maturity of 2.7 and 28 days.

 The results obtained are recorded in Table (II).

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Table (II) Mechanical Characterization of Concrete Paving Formulations Containing Phenolic Derivatives.

<Tb>

Concrete <SEP> control <SEP> + 0.5% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1%
<tb> GLENIUM <SEP> 27 <SEP> TIRON <SEP> CATECHOL <SEP> ACID <SEP> 5-A. <SEP> SA
<Tb>

SALICYLIC
<tb> at / f <SEP> at <SEP> 2 <SEP> days <SEP> 3.7 <SEP> 4.3 <SEP> 4.2 <SEP> 3.8 <SEP> 3.5 <SEP > 3,5
<tb>#cs<SEP> to <SEP> 2 <SEP> days <SEP> 19.5 <SEP> 20.6 <SEP> 20.7 <SE> 19.5 <SE> 17.4 <SEP> 16.5
<tb># t / f <SEP> to <SEP> 7 <SEP> days <SEP> 6.9 <SEP> 7.3 <SEP> 7.1 <SEP> 7.0 <SEQ> 6.8 <SEP> 6.5
<tb> acsà7days <SEP> 40.4 <SEP> 38.1 <SEP> 47.4 <SEP> 42.1 <SEP> 39.7 <SEP> 41.7
<tb># t / f <SEP> to <SEP> 28 <SEP> days <SEP> 6.8 <SEP> 7.5 <SEP> 7.7 <SEP> 7.2 <SEQ> 7.4 <SEP> 7.9
<tb>#cs<SEP> to <SEP> 28 <SEP> days <SEP> 44.5 <SEP> 49.1 <SEP> 55.0 <SEP> 51.6 <SEP> 53.7 <SEP> 55.1
<Tb>
# t / g: Flexural tensile tensile stress [MPa].

#cs: Breaking stress in simple compression [MPa].

<Desc / Clms Page number 24>

 5-A.S.A. leads to the best performance at the end of 28 days from the point of view of flexural tensile strength # t / f. All the additive concretes lead to higher performances than the control concrete (non-additive concrete).

 Regarding the simple compressive strength these, we observe that the TIRON achieves the best performance, regardless of the measurement deadline.

 The 5-A.S.A gives equivalent results, with a maturity of 28 days.

3. Effect on the density of hardened matrices
Density measurements were made on fresh dough (po density) by weighing calibrated containers. (primsatic specimens of dimensions 7 x 7 x 28 cm3).

 The density of the hardened test specimens (#s) was measured at 1, 2, 7 and 28 days after the specimens had been removed from their storage water, dried on the surface using a paper towel, and then packaged for 3 hours in the open air.

 The values obtained are recorded in Table (III).

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Table (III) Density measurements (# 0; #s) made on paving concrete formulations, containing phenolic derivatives,

<tb> Concrete <SEP> + 0.5% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1% <SEP> + 0.1%
<tb> control <SEP> GLENIUM <SEP> 27 <SEP> TURN <SEP> CATECHOL <SEP> ACID <SEP> 5-A. <SEP> SA
<Tb>

SALICYLIC
<tb> Density <SEP> Fresh <SEP># 0 <SEP> 2.31 <SEP> 2.19 <SEP> 2.41 <SEP> 2.33 <SEP> 2.26 <SEP> 2.30
<tb> Density <SEP> ps <SEP> to <SEP> 1 <SEP> day <SEP> 2.37 <SEP> 2.31 <SEP> 2.36 <SEP> 2.38 <SE> 2.37 <SEP> 2.32
<tb> Density <SEP> ps <SEP> to <SEP> 2 <SEP> days <SEP> 2.33 <SEP> 2.30 <SEP> 2.32 <SEP> 2.38 <SEP> 2.33 <SEP> 2.28
<tb> Density <SEP> ps <SEP> to <SEP> 7 <SEP> days <SEP> 2.40 <SEP> 2.33 <SEP> 2.41 <SEP> 2.39 <SEP> 2.39 <SEP> 2.36
<tb> Density <SEP> ps <SEP> to <SEP> 28 <SEP> days <SEP> 2.39 <SEP> 2.34 <SEP> 2.37 <SEP> 2.39 <SEP> 2.40 <SEP> 2.33
<Tb>

<Desc / Clms Page number 26>

It is observed that the TIRON leads to the highest density values during the first measurement periods.

 At the end of the first 28 days of hydration, the density of the adjuvant concrete with the TIRON is slightly lower than that of the control concrete, although the mechanical performance is clearly in favor of the first.

 This seems to be the sign of the formation of more resistant phases, or of a particular modification of the microstructure (crystalline stacking, etc.) of the material, tending to improve its mechanical performance.

Example 2
Tests on smoothing coating formulas "
The working formula is as follows

<Tb>
<tb> - <SEP> CPA <SEP> CEM <SEP> I <SEP> 52.5 <SEP> LAFARGE <SEP>"<SEP> St <SEP> VIGOR <SEP>"<SEP> 24.7 <SEP > g <SEP> (73 <SEP>% <SEP> of <SEP> weight <SEP> of <SEP> binding)
<tb> - <SEP> Aluminous <SEP> Cement <SEP> T. <SEP> RG <SEP> LAFARGE <SEP> 9.0 <SEP> g <SEP> (27 <SEP>% <SEP> of <SEP > weight <SEP> of <SEP> binding)
<tb> - <SEP> Casein <SEP> 0 <SEP> or <SEP> 0.5 <SEP> g
<tb> - <SEP> DURCAL <SEP> 65 <SEP> (OMYA) <SEP> 19,875 <SEP> g
<tb> - <SEP> Lime <SEP> extinguished <SEP> Ca (OH) 2 <SEP> 2.95 <SEP> g
<tb> - <SEP> Sand <SEP> NE <SEP> 03 <SEP> (SIFRACO) <SEP> 40.6 <SEP> g
<tb> - <SEP> TYLOSE <SEP> 200 <SEP> XP <SEP> (HOECHST) <SEP> 0.1 <SEP> g
<tb> - <SEP> BEVALOID <SEP> 770 <SEP> DD <SEP> 0.15 <SEP> g <SEP>
<tb> - <SEP> Trisodium citrate <SEP><SEP> 0.125 <SEP> g <SEP>
<tb> - <SEP> RHOXIMAT <SEP> PAV <SEP> 30 <SEP> 2 <SEP> g <SEP>
<tb> - <SEP> Water <SEP> of <SEP> mixing <SEP> 24 <SEP> parts
<Tb>

Phenolic derivatives were used at levels of 0.1 or 0.2% by weight of binder (CPA + CA).

 The results obtained are recorded in Tables (IV) and (V)

<Desc / Clms Page number 27>

Table (IV) Characteristics of Adjuvant Smoothing Coatings of Phenolic Derivatives.

<Tb>
<Tb>

Binder: <SEP> Etals <SEP> (mm) <SEP> Take <SEP> VICAT
<tb> N <SEP> 73 <SEP>% <SEP> CPA <SEP> - <SEP> 5 <SEP> min <SEP> 15 <SEP> 25 <SEP> min <SEP> 35 <SEP> min <SEP > Start <SEP> of <SEP> End <SEP> of
<tb> 27 <SEP>% <SEP> TRG <SEP> min <SEP> take <SEP> rise
<tb> 1 <SEP> Control <SEP> 80 <SEP> 70 <SEP> / <SEP> / <SEP> 58 <SEP><SEP> 1 <SEP> h <SEP> 10 <SEP>
<tb> (without <SEP> casein)
<tb> 2 <SEP> Control <SEP> 135 <SEP> 116 <SEP> 96 <SEP> / <SEP> 58 <SEP><SEP> 1 <SEP> h <SEP> 16 <SEP>
<tb> (with <SEP> 0.5 <SEP>% <SEP> @
<tb><SEP> Casein) <SEP><SEP> Assay <SEP> Sclerometer <SEP> Good
<Tb>

Table (V) Characteristics of Adjuvant Smoothing Coatings of Phenolic Derivatives.

<Tb>
<Tb>

Binder: <SEP> Etals <SEP> (mm) <SEP> Take <SEP> VICAT
<tb> N <SEP> 90 <SEP>% <SEP> CPA <SEP> - <SEP> 5 <SEP> min <SEP> 15 <SEP> min <SEP> 25 <SEP> min <SEP> 35 <SEP > Start <SEP> of <SEP> End <SEP> of
<tb> 10 <SEP>% <SEP> TRG <SEP> min <SEP> taken <SEP> taken
<tb> 3 <SEP> Control <SEP> 135 <SEP> 135 <SEP> 132 <SEP> 120 <SEP> 52 <SEP> minutes <SEP> 1 <SEP> h <SEP> 08 <SEP>
<tb> (0.5 <SEP>% <SEP> casein <SEP> at <SEP> Sclerometer <SEP> Wrong ~~~~~~~
<tb> 4 <SEP> + <SEP> 0.2 <SEP>% <SEP> 128 <SEP> 112 <SEP> 70 <SEP> 1 <SEP> h <SEP> 1 <SEP> h <SEP> 15 <September>
<tb> CATECHOL <SEP> Test <SEP> at <SEP> Sclerometer <SEP> Good <SEP> idemFormula <SEP> 2)
<Tb>

It is observed that, when using CATECHOL, it is possible to reduce the dosage of aluminous cement. It becomes possible according to the invention to pass from a dosage of 27%, in the reference formulations, to a dosage of 10% in the formulas of the invention.

 The interest lies in the improvement of mechanical performance, related to the lowering of the alumina cement dosage (used in combination with Portland cement).

Example 3
Tests on "tiling mortar" formulas
The job formulation is as follows

<Tb>
<tb> - <SEP> CPA <SEP> CEM <SEP> I <SEP> 52.5 <SEP> LAFARGE <SEP>"SEP>SEV>SEP>SEP> 36.2 <SEP> g
<tb> - <SEP> Sand <SEP> EN <SEP> 31 <SEP> (SIFRACO) <SEP> 58.3 <SEP> g
<Tb>

<Desc / Clms Page number 28>

<Tb>
<tb> - <SEP> CULMINAL <SEP> 8121 <SEP> (AQUALON) <SEP> 0.2 <SEP> g <SEP>
<tb> - <SEP> CULMINAL <SEP> 8564 <SEP> (AQUALON) <SEP> 0.3 <SEP> g
<tb> - <SEP> RHOXIMAT <SEP> PAV <SEP> 30 <SEP> 5 <SEP> g <SEP>
<tb> - <SEP><SEP><SEP><SEP><I / O><SEP> 24 <SEP> Ratios
<Tb>

The phenolic adjuvants used (at a level of 0.2% by weight of binder) are the following: - TIRON - SALICYLIC ACID - CATECHOL - 5-ASA
The results obtained are recorded in Table (VI)
Table (VI)
Characteristics of adhesive mortars for adjuvant tiling of phenolic derivatives

<Tb>
<tb> N <SEP> Formulation <SEP> Density <SEP> Viscosity * <SEP> Slip
<tb> CPA <SEP> CEM <SEP> 152.5 <SEP> Fresh <SEP># 0 <SEP> (cPs) <SEP> (mm)
<tb>"St<SEP> Vigor <SEP>"
<tb> 1 <SEP> Control <SEP> 1.50 <SEP> 128 <SEP> 000 <SEP> 7.0
<tb> 2 <SEP> + <SEP> 0.2 <SEP>% <SEP> TURN <SEP> 1.50 <SEP> 148 <SEP> 000 <SEP> 3.5
<tb> 3 <SEP> + <SEP> 0.2 <SEP>% <SEP> SALICYLIC <SEP>SEP>SEP> 1.50 <SEP> 144 <SEP> 000 <SEP> 3.5
<tb> 4 <SEP> + <SEP> 0.2 <SEP>% <SEP> CATECHOL <SEP> 1.59 <SEP> 168 <SEP> 000 <SEP> 2.0
<tb> 5 <SEP> + <SEP> 0.2 <SEP>% <SEP> 5-ASA <SEP> 1.50 <SEP> 140 <SEP> 000 <SEP> 5.0
<Tb>
* Measurements made with BROOKFIELD viscometer "HELIPATH", at 20 t / min
CATECHOL significantly reduces slippage of tiles (increase of viscosity). This effect is even clearer, when the mortiercolle does not contain latex powder [Cf. table (VII)]: the viscosity of the paste rose from 120,000 cPs to a value of 188,000 cPs (+ 57%).

<Desc / Clms Page number 29>

Table (VII) Confirmation of the Effect of CATECHOL on the Density of a Formula of Latex-Free Adhesive.

<Tb>
<Tb>

Density <SEP> Fresh <SEP># 0 <SEP> Viscosity * <SEP> (cPs)
<tb> Witness <SEP> 1.68 <SEP> 120 <SEP> 000 <SEP>
<tb> + <SEP> 0.2 <SEP>% <SEP> CATECHOL <SEP> 1.76 <SEP> 188000
<Tb>
* Measurements made with the BROOKFIELD viscometer "HELIPATH", at 20 rpm.

It can therefore be deduced that it is possible to lower the level of viscosity agent used in the basic formula, without this adversely affecting the properties of mortar use.
Regarding the adhesion characteristics of the tiles (resistance to tearing), Table (VIII) summarizes the results obtained.

Table (VIII)
Characteristics of adjuvant adhesive mortars of phenolic derivatives
1. Adhesion measures after 7 days dry
2. Measurements after 7 days dry and 7 days in the water

<Tb>
<tb> Density <SEP> Viscosity * <SEP> Adhesion <SEP> in <SEP> MPa <SEP> Adhesion <SEP> in <SEP> MPa
<tb> fresh <SEP> (7 <SEP> to <SEP> sec) <SEP> (7 <SEP> j <SEP> to <SEP> sec <SEP> - <SEP> 7 <SEP> j <SEP> water)
<tb># 0 <SEP> (cPs) <SEP> 5 <SEP> min <SEP> 10 <SEP> min <SEP> 5 <SEP> min <SEP> 10 <SEP> min
<tb> Control <SEP> 1.53 <SEP> 150 <SEP> 000 <SEP> 1.64 / <SEP> 1.23 / <SEP> 0.45 / <SEP> 0.33 /
<tb> A <SEP> A <SEP> A <SEP> A
<tb> + 0.2% <SEP> 1.47 <SEP> 128 <SEP> 000 <SEP> 1.72 / <SEP> 1.70 / <SEP> 1.0 / <SEP> 0.78 /
<tb> ACID <SEP> C ++ <SEP> C + <SEP> C ++ <SEP> A
<tb> SALICYLIC
<Tb>
* Measurements made with the BROOKFIELD "HELIPATH" viscometer, at 20 rpm A: "Adhesive" fracture C: "Cohesive" fracture
The addition of a compound such as SALICYLIC ACID improves the values of resistance to tearing, the break is in a "cohesive" mode, which goes in a positive direction.

<Desc / Clms Page number 30>

Example 4
Associations "phenolic derivatives / precipitated silica"
In the tests, amorphous SiO 2 precipitated silica, presented in the form of slurry at 22% solids content (RHOXIMAT CS 60 SL), is combined with phenol derivatives in proportions of "30 parts / 1 part".
Once the mixtures are made, their properties of use are evaluated in standardized mortar formulations (ISO 1/3 mortars), the details of which are as follows.

<Tb>
<Tb>

- <SEP> CPA <SEP> CEM <SEP> I <SEP> 52.5 <SEP> LAFARGE <SEP>"<SEP> St <SEP> VIGOR <SEP>"<SEP> 450 <SEP> g
<tb> - <SEP> Sand <SEP> normalized <SEP> (compliant <SEP> ISO <SEP> 679) <SEP> 1350 <SEP> g
<tb> - <SEP> Water <SEP> [E / C <SEP> = <SEP> 0.50] <SEP> 225 <SEP> g <SEP>
<Tb>

"Mixed" precipitates of precipitated silica slurry (adjuvanted phenol derivatives) are used at 3%, based on the weight of cement.

 Once the mortars are made (mixing with the PERRIER Type 32 standard mixer), their rheological characteristics are studied from the point of view of the spreading at the shaking table (according to EN 459-2 and ISO 2768-1 standards).

 The results obtained are recorded in Table (IX).

<Desc / Clms Page number 31>

Table (IX) Rheological characteristics of the adjuvanted standard mortars with mixed suspensions "Si02 precipitated silica / phenol derivatives".

<Tb>
<Tb>

+ 3% <SEP> + 3% <SEP> + 3% <SEP> + 3% <SEP> + 3%
<tb> Etals <SEP> Mortar <SEP>"<SEP> CS <SEP> 60 <SEP> Slurry <SEP> Joint <SEP> Slurry <SEP> Slurry <SEP> Joint <SEP> Slurry
<tb> relative * <SEP> Control <SEP> SL <SEP>"<SEP> Si02 <SEP> / <SEP> mixed <SEP>" SiO2 <SEP> / <SEP> 5- <SEP> mixed
<tb> (%) <SEP> CATECHOL <SEP>"<SEP> Si02 <SEP>ASA"<SEP>"<SEP> Si02 <SEP>
<tb> TIRON <SEP> ACID
<tb> SALICYLI
<tb> THAT "
<tb> Spreading
<tb> at <SEP> tip <SEP> of <SEP> 0% <SEP> 0% <SEP> 0% <SEP> 0% <SEP> 0% <SEP> 0%
<tb> 0 <SEP> shocks
<tb> Spreading
<tb> at the <SEP> tip <SEP> of <SEP> 25% <SEP> 20 <SEP>% <SEP> 5% <SEP> 30 <SEP>% <SEP> 25% <SEP> 30 <SEP> % <SEP>
<tb> 5 <SEP> shocks
<tb> Spreading
<tb> at the <SEP> tip <SEP> of <SEP> 45% <SEP> 35% <SEP> 20 <SEP>% <SEP> 50 <SEP>% <SEP> 50 <SEP>% <SEP> 55 %
<tb> 10 <SEP> shocks
<tb> Spreading
<tb> at <SEP> tip <SEP> of <SEP> 55% <SEP> 50 <SEP>% <SEP> 30 <SEP>% <SEP> 65% <SEP> 70 <SEP>% <SEP> 75 %
<tb> 15 <SEP> shocks
<Tb>
* (Dx shocks - Do / Do) x 100
When adding the silica slurry "RHOXIMAT CS 60 SL" alone, at a dosage of 3% of the weight of cement (knowing that the mixing ratio "E / C" has been kept constant), there is a decrease the plasticity of the dough
On the other hand, when the silica slurry is associated with products of the TIRON, 5-ASA or SALICYLIC ACID type, the spreading values are improved, both with respect to the control mortar (without adjuvant), and with respect to mortar containing the slurry "RHOXIMAT CS 60 SL" only Example 5:
Associations "phenolic compounds / super-plasticizers
By way of example, mention may be made of the following super-plasticizers - GLENIUM # 51 (MBT - SKW)

<Desc / Clms Page number 32>

- CHRYSOFLUID # OPTIMA 100 (CHRYSO - LAFARGE)
The proportions adopted are as follows. 10 parts of "superplasticizer" / 1 part "phenolic compound"
The objective is to improve the rheological properties, while benefiting from the resistance gain generated by the phenolic compound (Table II).

The rheological evaluation was carried out on an ISO 1/3 mortar, the mixing rate of which was set at a value E / C = 0. 35, for the purpose of the study
The spreading values obtained are as follows.

Paintings)
Associations "phenolic compounds / superplasticizers".

Spreading tests at the shaking table

<Tb>
<tb> Witness <SEP> + <SEP> Witness
<tb> Number <SEP> of <SEP> shocks <SEP> 1% <SEP> GLENIUM # <SEP> 51 <SEP> + <SEP> 1% <SEP> (GLENIUM # <SEP> 51 <SEP> / <SEP> ASA)
<tb> 0 <SEP> 100 <SEP> 100
<tb> 5 <SEP> 105 <SEP> 108
<tb> 10 <SEP> 115 <SEP> 120
<tb> 15 <SEP> 128 <SEP> 130
<Tb>

Claims (37)

1 - Adjuvant composition for inorganic binders characterized in that it comprises at least one phenolic derivative. 2 - Composition according to claim 1 characterized in that the phenolic derivative is any aromatic compound, preferably benzene bearing at least one hydroxyl group in free form or functionalized and carrying at least one other group comprising an atom of oxygen and / or nitrogen and / or sulfur: said group may be carried by the aromatic ring or be part of the functional group attached to the oxygen atom. 3 - Composition according to one of claims 1 and 2 characterized in that the phenolic derivative used corresponds to formula (I):

 in said formula (I): Y1 represents: a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, an R group which may be a linear or branched alkyl group having 1 to 12 carbon atoms or an alkenyl group or alkynyl having 2 to 12 carbon atoms bearing an ionizable group G in acid or safed form such as a carboxylic, carboxylate, sulphonic, sulphonate, hemisulfuric, sulphate, phosphonic, phosphonate, hemiphosphoric, phosphate group in acid form or salified,. a group of formula (F):

 (F) in which the groups R1 and R2, which are identical or different, represent a hydrogen atom, a methyl or ethyl group: when one of the groups R1 or R2 is a methyl or ethyl group, the other group R1 or R2 is then a hydrogen atom and m is a number between 1 and 50. <Desc / Clms Page number 34> X1 represents: a group -O-Y2, Y2, identical or different from Y1, having the same meaning, a linear or branched alkyl group having 1 to 18 carbon atoms, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dry butyl, tert-butyl, dodecyl, hexadecyl, octadecyl; . a linear or branched alkenyl group having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl, a linear or branched alkoxy group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, an alkenyloxy group, preferably an allyloxy group or a phenoxy group,. an acyl group of formula R3-CO- in which R3 represents a linear or branched alkyl group having from 1 to 17 carbon atoms, preferably acetyl, lauroyl, palmitoyl, stearoyl, a group = 0,. a -CHOH-COOH group, a group of formula: -R4-OH-R4-COOR5 -R4-COOM-R4-CHO-R4-NO2-R4-NH2-R4-CO-NH2-R4-NH-CH2-CH2-OH-R4- N- [CH2-CH2-OH] 2 in said formulas, R4 represents a valency bond or a linear or branched divalent hydrocarbon group, saturated or unsaturated, having from 1 to 6 carbon atoms such as, for example, methylene, ethylene propylene, isopropylene, isopropylidene; the groups R5 which are identical or different represent a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms, a metal cation, preferably an alkaline cation or an ammonium group, <Desc / Clms Page number 35>  . a group -SO3M in which M represents a hydrogen atom or a metal cation, preferably an alkaline cation or an ammonium group, - two X groups carried on two vicinal carbon atoms or two OY1 and X1 groups on two atoms vicinal carbon may be linked by a methylenedioxy or ethylenedioxy bridge, - if n is 0, Y1 is R, - if Y1 is hydrogen, n is at least 1.  n is a number ranging from 0 to 5, preferably equal to 1, 2 or 3. 4 - Composition according to claim 3 characterized in that the phenolic derivative corresponds to the formula (I) wherein Y1 represents a hydrogen atom, and X1 represents a formyl group or a carboxylic group. 5 - Composition according to claim 3 characterized in that the phenolic derivative corresponds to formula (I) wherein the Y1 group represents an oxyalkylenated group of formula (F) in which the R2 group represents a hydrogen atom or a group methyl and the group R1 represents a hydrogen atom. 6 - Composition according to Claim 3, characterized in that the phenolic derivative corresponds to formula (1) in which the group Y1 represents an oxyalkylenated group of formula (F1):

 In which lacquer are numbers P q (F1) in which p and q are numbers such that: p + q = ## EQU1 ## m, -p + q1, p is 0 to 5, q is 0 to 10. 7 - Composition according to one of claims 5 and 6 characterized in that the phenolic derivative is an oxyalkylenated phenol derivative corresponding to formula (I) wherein X1 represents one or two sulphonic groups in salified form, preferably in the form an alkali metal, <Desc / Clms Page number 36>  (preferentially sodium or potassium), alkaline earth or an ammonium group. 8 - Composition according to claim 1 characterized in that the phenolic derivative is chosen from: diphenol compounds, precursor vanillins and derivatives, salicylates, phenolic compounds nitrogen. 9 - Composition according to claim 1 characterized in that the phenolic derivative is chosen from: - phenoxyacetic acid.  the diphenolic compounds, pyrocatechol,. resorcinol,. 1,4-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, Sodium 4,5-dihydroxybenzene-1,3-disulfonate, Sodium 2,5-dihydroxybenzene-1,4-disulfonate, Sodium 4,5-bis (2-hydroxyethoxy) benzene-1,3-disulfonate,. Sodium 4,5-bis (2-hydroxy-1-propoxy) benzene-1,3-disulfonate, Sodium 4,6-bis (2-hydroxyethoxy) benzene-1,3-disulfonate, 3,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzoquinone,. 2,6-dinitro-4-methoxyphenol,. 4-amino-1,2-dihydroxybenzene, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzoic acid, 2-hydroxyphenoxyacetic acid.  . methylenedioxybenzene, - nitrogenous phenolic compounds.  . 2-aminophenol, 3-aminophenol,. 2-amino-1- (2-hydroxyethoxy) benzene, <Desc / Clms Page number 37>  . 3-amino-1- (2-hydroxyethoxy) benzene, 2-amino-o-cresol, 3-amino-o-cresol, 6-amino-m-cresol - vanillin precursors,. the guetol,. vanillomandelic acid,. orthovanillomandelic acid,. the mandelic acid of catechol, methylenedioxybenzenemandelic acid,. p.trifluoromethylmandelic acid,. 2,6-difluoromandelic acid, vanillins and derivatives, vanillin,. ethyl vanillin; . orthovanillin,. isovanillin,. the veratric aldehyde,. veratric acid,. vanillic acid,. orthovanillic acid,. isovanillic acid,. vanillin and its isomers in the form of sulphite, - salicylates,. salicylic aldehyde,. salicylic acid,. 5-nitrosalicylic acid, 5-aminosalicylic acid, sodium salt of 5-sulfosalicylic acid,. 5-chlorosalicylic acid,. 5-methylsalicylic acid,. O-acetylsalicylic acid,. salicylamide,. 2-hydroxyethoxy-4-hydroxybenzoic acid, 2-hydroxyethoxy-4-sodiooxysulfonylbenzoic acid. 10 - Composition according to one of claims 1 to 9 characterized in that the phenol derivative is used in an amount representing 0.05 <Desc / Clms Page number 38>  at 3%; preferably from 0.1 to 0.3% by weight of the binder expressed as solids.  11 - Composition in powder form, characterized in that it comprises at least one phenolic derivative described in one of claims 1 to 9 and an amorphous silica, preferably a precipitated silica.  12 - Process for the preparation of the composition described in claim 11, characterized in that the dry phenolic derivative in powder form and a silica in the form of powder are dry blended. 13 - Aqueous suspension of amorphous silica characterized in that it comprises at least one phenolic derivative described in one of claims 1 to 9. 14 - aqueous suspension according to claim 13, characterized in that the amorphous silica is a precipitated silica. 15 - aqueous suspension according to one of claims 13 and 14 characterized in that the amorphous silica content is between 1 and 60% by weight, preferably between 1 and 49% by weight, and even more preferably between 3 and 35% by weight relative to the total weight of the suspension. 16 - aqueous suspension according to one of claims 13 to 15 characterized in that the phenolic derivative is present in an amount representing 0.5 to 5% by weight, and preferably at least 1% by weight relative to to the total weight of the suspension. 17 - Process for the preparation of the aqueous suspension of silica described in one of Claims 13 to 16, characterized in that it consists of either mixing, with stirring, at least one amorphous silica, in the form of a powder, with minus one phenolic derivative, in the form of a powder, and water, or mixing, with stirring, at least one amorphous silica, in the form of a powder, with an aqueous solution of at least one phenolic derivative, and optionally with the water, or mixing, with stirring, an aqueous suspension of at least one amorphous silica, with at least one phenolic derivative in the form of a powder, and possibly with water, <Desc / Clms Page number 39>  or mixing, with stirring, an aqueous suspension of at least one amorphous silica, with an aqueous solution of at least one phenolic derivative, and optionally with water.  18 - Process for preparing concrete characterized in that the aqueous suspension is added to the concrete according to one of claims 13 to 16.  19 - Process according to claim 18 characterized in that the aqueous suspension is added to the concrete in a proportion of 0.1 to 15% by weight, more preferably 2.5 to 5% by weight of cement put in place. to prepare the concrete. 20 - Process according to claim 19 characterized in that the addition of the aqueous suspension is at the time of mixing the concrete, or in the mixing water. 21 - Composition in powder form, characterized in that it comprises at least one phenolic derivative described in one of Claims 1 to 9 and at least one resin in the form of a powder. 22 - Composition according to Claim 21, characterized by the fact the resin is a styrene-butadiene copolymer, a vinyl ester (s) copolymer (s), a vinyl acetate (co) polymer; an ethylene acetate (co) polymer, a copolymer of vinyl acetate and at least one vinyl ester of saturated monocarboxylic acids, branched or unbranched, having 1 to 12 carbon atoms, a copolymer a vinyl ester and at least one unsaturated mono- or di-carboxylic acid ester having 3 to 6 carbon atoms and alkyl having 1 to 10 carbon atoms. 23 - Process for preparing the composition described in one of claims 21 and 22, characterized in that it consists in dry blending at least one phenolic derivative in powder form and a resin in powder form 24 - Emulsion aqueous solution of at least one (co) polymer resin (latex) characterized in that it comprises at least one phenolic derivative described in one of claims 1 to 9. <Desc / Clms Page number 40> Latex according to claim 24, characterized in that the resin is a styrene-butadiene copolymer, a vinyl ester (s) copolymer (s), a vinyl acetate (co) polymer; an ethylene acetate (co) polymer, a copolymer of vinyl acetate and at least one vinyl ester of saturated monocarboxylic acids, branched or unbranched, having 1 to 12 carbon atoms, a copolymer a vinyl ester and at least one unsaturated mono- or di-carboxylic acid ester having 3 to 6 carbon atoms and alkyl having 1 to 10 carbon atoms. 26 - Latex according to one of claims 24 and 25 characterized in that the resin is present in an amount of between 5 and 60% by weight, preferably between 10 and 50% by weight, relative to the total weight of the suspension. 27 - Latex according to one of claims 24 to 26 characterized in that the phenolic derivative is present in an amount ranging from 0.1 to 10% of the resin weight expressed as solids, preferably between 1 and 5% . 28 - Process for the preparation of a mortar characterized in that the composition described in one of claims 21 and 22 is introduced into the dry mix of hydraulic binder, granulates and other additives, and then the feed is introduced. water of gachage. 29 - Process for preparing a mortar characterized in that the latex described in one of claims 24 to 27 is introduced into the inorganic binder, then the mixture is kneaded together, and the aggregates, and continues mixing. 30 - Composition characterized in that it comprises at least one phenolic derivative described in one of claims 1 to 9 and at least one superplasticizer. 31 - Composition according to claim 30 characterized in that it comprises: - from 10 to 90% by weight of at least one phenolic derivative, - from 10 to 90% by weight of at least one superplasticizer. 32 - Composition according to one of claims 30 and 31 characterized in that the superplasticizer is selected from condensates of naphthalene type <Desc / Clms Page number 41>  sulfonate, melamine sulfonate, alkali and alkaline earth metal polycarboxylates; polyacrylates of alkali and alkaline earth metals; alkylene polyoxides optionally grafted with a complexing group of calcium or their derivatives, optionally in combination with an aminoalkylene phosphonate; derivatives of polymers or copolymers based on acrylic or methacrylic acid, and terpolymers of acrylic or methacrylic acid or their salts. 33 - Composition according to one of claims 30 to 32 characterized in that it is in the form of powder. 34 - Composition according to one of claims 30 to 32 characterized in that it is in the form of an aqueous suspension. 35 - Composition according to claim 34 characterized in that the solids content of the suspension is 20 to 50% by weight. 36 - Composition according to one of claims 30 to 35 characterized in that it is carried out in an amount representing 0.5 to 5% of the weight of the cement. 37 - Use of at least one phenolic derivative according to one of claims 1 to 9 in a medium of the cement matrix type, concrete or mortar, as agent improving the fluidity of the dough, without causing air. 38 - Use of at least one phenolic derivative according to one of claims 1 to 9 in a medium of the cement matrix type, concrete or mortar, as an agent increasing the mechanical properties of concretes and mortars obtained 39 - Use of at least one phenolic derivative described in one of claims 1 to 9 in a smoothing coating as an agent for reducing the level of aluminous cement in binary or ternary mixtures, while keeping an acceptable open time, and improved mechanical properties . 40 - Use of an aqueous suspension described in one of claims 13 to 16 in a medium of the cement matrix type, concrete or mortar, as agent improving the cohesion of said medium. <Desc / Clms Page number 42> 41 - Cementitious matrices, concretes and mortars comprising at least one phenolic derivative described in one of Claims 1 to 9.