Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
  • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
  • C04B40/0039—Premixtures of ingredients
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
  • C04B2103/52—Grinding aids; Additives added during grinding
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate

Definitions

• the present invention relates to the use during manufacture of the cement of a composition comprising at least one sacrificial molecule in order to protect the dispersants during the grinding of the clinker.
• the dispersants are generally organic molecules, for example polymers.
• One of their uses may be the fluidification of hydraulic compositions or other mineral fillers. In practice, they are most often added to the hydraulic compositions or to other mineral fillers during the mixing phase, either in the mixing water or at the same time as the various components.
• the dispersants undergo a reduction or even a total loss of their fluidizing power when they are subjected to grinding. This effect of grinding on the effectiveness of the dispersants does not allow the dispersants to be added to a cement when the latter is being grinded.
• the problem to be solved by the invention is to provide a new means adapted to protect dispersants against a partial or total reduction of their fluidizing power during grinding during the manufacture of cement, that is to say to maintain in part or in all their fluidizing properties during grinding.
• the present invention proposes the use during the manufacture of the cement of a composition comprising at least one dispersant and a sacrificial molecule to maintain all or part of the properties of the dispersant, the composition
• the amount of the sacrificial molecule in the composition representing at least 5% by weight of the dispersant mass; and being introduced before or during the grinding of the clinker.
• the invention has the advantage of being implemented in all industries using a grinding process, including the building industry, the chemical industry (adjuvant), the cement industry, or the grinding stations.
• sacrificial molecule By the expression “sacrificial molecule” according to the present invention is meant a molecule capable of operating in one of the two following ways in order to maintain all or part of the fluidizing properties of a dispersant when it is subjected to grinding: either degrade in place of the dispersant or react with the dispersant so as to protect it. Preferably, the sacrificial molecule degrades in place of the dispersant.
• a preferred sacrificial molecule is an antioxidant.
• antioxidant according to the present invention is understood to mean a molecule suitable for capturing electrons or free radicals and then stabilizing.
• the term "dispersant” according to the present invention is understood to mean an organic molecule used in the field of hydraulic compositions or other mineral fillers in order to fluidize said hydraulic compositions or said other mineral fillers.
• a dispersant according to the present invention may especially be a plasticizer / water reducer or a superplasticizer / high water reducer as defined in the standard EN 934-2 in paragraphs 3.2.2 and 3.2.3.
• the fluidity of a hydraulic composition can in particular be evaluated by measuring the spreading according to the protocol described below.
• polyethylene oxide / propylene polycarboxylate or "PCP” according to the present invention is understood to mean a copolymer of acrylic and / or methacrylic acids, their ethylene oxide / propylene oxide (POE / POP) esters, or of their POE / POP ethers.
• POE / POP ethylene oxide / propylene oxide
• polyethylene oxide / propylene means in the present description polyethylene oxide, or polyethylene oxide and propylene.
• grinding the operation of dividing a solid, to reduce the size of the particles and / or to increase their specific surface area (developed surface of the powder per unit mass).
• hydraulic composition a composition which comprises a hydraulic binder.
• the hydraulic composition is a mortar or a concrete.
• hydraulic binder is understood to mean, according to the present invention, a compound having the property of hydrating in the presence of water and whose hydration allows to obtain a solid having mechanical characteristics.
• the hydraulic binder is a cement.
• cement means cements as defined in EN 197.1 and aluminous cements.
• the cement is a Portland cement.
• clinker according to the present invention is understood to mean the product obtained after firing (the clinkerization) of a mixture (raw material) composed, inter alia, of limestone and, for example, clay.
• a mixture composed, inter alia, of limestone and, for example, clay.
• the clinker is a Portland clinker as defined in standard NF EN 197.1.
• mineral fillers means any mineral product in the form of powder, the use of which may require the presence of a dispersant and / or which may be used in a hydraulic composition.
• emulsion means a homogeneous mixture of two immiscible liquid substances, a substance being dispersed in the second substance in the form of small droplets whose size is of the order of one micrometer.
• centimeter a colloidal dispersion in which a finely divided product, in liquid or solid form, is combined with another product in liquid form, the first product being in the form of droplets or particles of which the size is greater than one micrometer but small enough so that said first product does not redeposit quickly.
• An object according to the present invention is the use during manufacture of the cement of a composition comprising at least one dispersant and a sacrificial molecule to maintain all or part of the properties of the dispersant, the composition
• the amount of the sacrificial molecule in the composition representing at least 5% by weight of the dispersant mass
• an object of the invention is the use of at least one sacrificial molecule said sacrificial molecule being adapted either to degrade in place of the dispersant or to react with the dispersant so as to protect it.
• the dispersant and the sacrificial molecule are in the form of a liquid solution.
• the dispersant and the sacrificial molecule are not in the form of a solid solution.
• the dispersant and the sacrificial molecule are not added separately. In other words, they are not added sequentially. They are preferentially added simultaneously.
• a variant of the object according to the present invention is the use during manufacture of the cement of a composition comprising at least one dispersant and at least one sacrificial molecule to maintain all or part of the properties of the dispersant, the composition
• the amount of the sacrificial molecule in the composition representing at least 5% by weight of the dispersant mass
• the sacrificial molecule may be present in an amount greater than or equal to 5%, preferably 10%, more preferably 15%, more preferably 20% by dry weight relative to the dry mass of the dispersant.
• the sacrificial molecule is soluble in a solution of the dispersant.
• the sacrificial molecule is chosen from antioxidants.
• An antioxidant may be a hydrogen donor, a hydroperoxide decomposer, an alkyl radical scavenger, or a reducing agent in an oxidation-reduction reaction.
• the antioxidant comprises a reactive group such as for example an OH group or an NH group, preferably associated with a phenolic or aromatic ring.
• the antioxidant may especially be chosen from the following compounds, alone or as a mixture:
• ascorbic acid sodium ascorbates, calcium ascorbates, 5-6-1 -ascorbic diacetyl acid, palmityl 6-1-ascorbic acid;
• formula 1 ascorbic acid citric acid, sodium citrates, potassium citrates and calcium citrates;
• gallic acid and its esters such as, for example, methyl gallate, propyl gallate, octyl gallate or dodecyl gallate;
• organic phosphorus compounds such as, for example, phosphites or phosphonites, such as the following compounds:
• TNPP tris (nonylphenyl) phosphite
• organosulfur compounds for example esters of 3,3-thiodipropionic acid or esters of sulphurous acid, with the exception of sulphurous acid salts;
• lactones acrylic bis-phenols, substituted benzofuranones
• the sacrificial molecule is chosen from phenols, polyphenols, phenolic acids and their associated esters, aromatic secondary amines, organophosphorus compounds, organosulfur compounds with the exception of sulphurous acid salts, organic acids. and their associated esters, hydroxylamines, reducing redox reactions, their associated salts and mixtures thereof.
• the sacrificial molecule is preferentially chosen from phenols, polyphenols, phenolic acids and their associated esters, aromatic secondary amines, hydroxylamines, their associated salts and their mixtures.
• the sacrificial molecule is chosen from hydroquinone, methyl gallate, propyl gallate, gallic acid and hydroxylamine.
• the sacrificial molecule is 4-methoxyphenol or else named MEHQ.
• the invention has for another object the use during the manufacture of the cement of a composition comprising at least one dispersant and at least 4-methoxyphenol to maintain all or part of the properties of the dispersant, the composition
• the amount of the sacrificial molecule in the composition representing at least 5% by weight of the dispersant mass
• the dispersant is chosen from polycarboxylates of polyethylene oxide / propylene, polynaphthalenesulfonates, lignosulphonates, polymelamines sulfonates and mixtures thereof.
• the dispersant is preferably a polycarboxylate of polyethylene oxide.
• the dispersant may be used in the form of a liquid
• the sacrificial molecule may be used in the form of a powder or a liquid
• the sacrificial molecule may be soluble in a solution of the dispersant.
• the solubility of the sacrificial molecule in a solution of the dispersant allows a homogeneous mixture of these two compounds which are then in the form of a liquid solution.
• the sacrificial molecule may not be soluble in a solution of the dispersant, and the dispersant and the sacrificial molecule may be used in the form of an emulsion or a suspension. In order to obtain a stable emulsion / suspension, it is possible to further use a stabilizer.
• the sacrificial molecule and the dispersant can be copolymerized.
• the dispersant is a polymer
• Antioxidant monomers can then be integrated by radical copolymerization in a PCP type structure.
• the monomers may be chosen from the molecules described in Table 1 below. Table 1: Antioxidant Monomers
• the dispersant may comprise one or more types of dispersants.
• the sacrificial molecule may comprise one or more types of sacrificial molecules.
• customary adjuvants may also be used with the dispersant and the sacrificial molecule, such as, for example, a setting accelerator, a set retarder or an anti-foam agent.
• the amount of sacrificial molecule is at least 5%, preferably at least 10%, even more preferably at least 15% by dry weight relative to the dry mass of the dispersant.
• the amount of sacrificial molecule is less than or equal to 40%, preferably less than or equal to 20% by dry weight relative to the dry mass of the dispersant.
• the concentration of the mixture comprising the sacrificial molecule and the dispersant in a cement is from 0.05 to 5% by weight relative to the mass of cement.
• the dosage of sacrificial molecule relative to the dispersant to be protected may be dependent on the nature of the sacrificial molecule and the nature of the dispersant.
• the composition comprising at least one sacrificial molecule and at least one dispersant may be used during the manufacture of the cement comprising mineral additions to maintain all or part of the properties of the dispersant.
• the mineral additions are added during the manufacture of the cement before or during the grinding of the clinker.
• the amount of mineral addition included with the clinker is from 10 to 70% of mineral additions, more preferably from 10 to 60%, still more preferably from 10 to 50%,% by weight relative to the total mass. clinker.
• Another object according to the invention is the use of a cement with the composition as described above for the manufacture of a hydraulic composition.
• Another object according to the invention is the use of a mineral filler as described above for the manufacture of a hydraulic composition.
• the sacrificial molecule and the dispersant have the same characteristics as those described in connection with the first use according to the invention.
• the spreading of a mortar is measured thanks to a mini cone of Abrams whose volume is 800 ml_.
• the dimensions of the cone are as follows:
• the cone is placed on a dried glass plate and filled with fresh mortar. He is then leveled. The lifting of the cone causes a collapse of the mortar on the glass plate. The diameter of the slab obtained is measured in millimeters +/- 5 mm. This is the spreading of the mortar.
• the dispersants which have been tested are PCP, and in particular a PCP resulting from a laboratory synthesis having 30% of MMPEG 1 100 ester level (methoxy polyethylene glycol methacrylate having a molar mass of 1100 g / mol), a PCP from a laboratory synthesis with 20% MMPEG 1 100 ester level, Premia 180 (Supplier: Chryso), Premia 196 (Supplier: Chryso), Optima 200 (Supplier: Chryso) and 'Optima 203 (Supplier: Chryso).
• PCPs resulting from a laboratory synthesis tested in the various examples of the present description were synthesized by radical polymerization in water between methacrylic acid and methoxy polyethylene glycol methacrylate having a molar mass of 1100 g / mol . Depending on the desired ester level, the initial amounts of the two monomers are changed.
• MMPEG1 100 Methoxy polyethylene glycol methacrylate (MMPEG1 100) (Supplier: Aldrich): 341.7 g
• transfer agent thioglycolic acid (ATG - Supplier: Aldrich): 5.780 g
• the procedure for manufacturing the tested PCP is as follows:
• the sacrificial molecules tested in the present example are methyl gallate, propyl gallate, hydroquinone, hydroxylamine and gallic acid (Supplier: Aldrich), 4-methoxyphenol (ECEM supplier).
• the cement was ground according to the protocol described below.
• the crusher which has been used is a crusher which can contain 5 kg of material to grind and having 60 kg of metal balls, at the rate of 27 kg of balls whose average diameter is between 40 and 60 mm, 18 kg of balls whose average diameter is between 25 and 35 mm and 15 kg of balls whose average diameter is between 20 and 25 mm.
• the mill was used at a speed of 40 rpm. The grinding steps are as follows:
• the cement was used for the manufacture of a mortar, for which rheology monitoring was carried out in order to highlight the effect of the sacrificial molecule.
• the formulation of the tested mortar is as follows:
• the cement is a cement CEM I 52.5 N.
• ISO sand is a siliceous sand (Supplier: ieri du Littoral).
• the mortar tested was manufactured according to the protocol described below:
• Tables 1 and 2 below present the results of tests carried out with different sacrificial molecules.
• the composition used according to the invention comprising at least one sacrificial molecule and at least one dispersant is either added during the grinding of a clinker or is added to a mortar (control).
• Table 1 Summary of the spreading tests carried out during the milling at 20 ° C. of a clinker in comparison with a control corresponding to the addition of the composition according to the invention to a mortar
• the effect of different sacrificial molecules has been demonstrated because the fluidizing power of the PCP subjected to grinding at 20 0 C is improved in the presence of a sacrificial molecule.
• the 5-minute spread of a mortar comprising a single PCP subjected to grinding at 20 ° C. is 220 mm, whereas it is 275 mm in the presence of 10% of methyl gallate, or of 285 mm in the presence of 20% of propyl gallate.
• Table 2 Summary of the spreading tests carried out during the grinding at 100 ° C. of a clinker in comparison with a control corresponding to the addition of the composition according to the invention to a mortar
• composition used according to the invention comprising at least one sacrificial molecule and at least one dispersant is either added during the grinding of a clinker or is added to a mortar (control).
• Table 3 Summary of the spreading tests carried out during the grinding at 100 ° C. of a clinker in comparison with a control corresponding to the addition of the composition according to the invention to a mortar
• the effect of a sacrificial molecule has been demonstrated on 5 different dispersants.
• the fluidizing power of the dispersants tested subjected to grinding at 100 0 C is improved in the presence of a sacrificial molecule.
• the spreading at 5 minutes of a mortar comprising a premia 180 subjected to a grinding to 100 0 C in the absence of a sacrificial molecule is 210 mm, while it is 275 mm in the presence of 20% of methyl gallate.
• the spreading at 5 minutes of a mortar comprising a PCP having 20% of MMPEG 1100 ester level subjected to grinding at 100 ° C. in the absence of a sacrificial molecule is 220 mm, whereas is 255 mm in the presence of 20% methyl gallate.
• the cement was ground according to the protocol described below.
• the crusher which has been used is a crusher which can contain 5 kg of material to grind and having 60 kg of metal balls, at the rate of 27 kg of balls whose average diameter is between 40 and 60 mm, 18 kg of balls whose average diameter is between 25 and 35 mm and 15 kg of balls whose average diameter is between 20 and 25 mm.
• the mill was used at a speed of 40 rpm. The grinding steps are as follows:
• Example 2 After grinding, the cement was used for the manufacture of a mortar (identical to that of Example 1), for which rheology monitoring was carried out in order to demonstrate the effect of the sacrificial molecule. Table 4 below presents the results of spreading tests carried out with different dispersants.
• the composition used according to the invention comprising at least one sacrificial molecule and at least one dispersant is either added during the grinding of a clinker or is added to a mortar (control).
• Table 4 Summary of the spreading tests carried out during grinding at 100 ° C. of a clinker in comparison with a control corresponding to the addition of the composition according to the invention to a mortar
• the minimum dosage of sacrificial molecule to provide dispersant protection during clinker milling is at least 5%.
• the best efficiency is obtained for a dosage of between 10 and 20%.
• Table 5 shows the results achieved spreading tests on different forms of use of the dispersant and the sacrificial molecule: liquid solution, dispersion of the sacrificial molecule in the dispersant and separate addition, during grinding at 100 0 C, and the results obtained.
• Table 5 Summary of the tests carried out to validate the form of use of the sacrificial molecule and the dispersant, during a milling at 100 ° of a clinker, and their results
• the sacrificial molecule and the dispersant must be in contact with one another before use.
• the fluidizing power of the dispersant subjected to grinding at 100 0 C is improved in the presence of a sacrificial molecule and a dispersant which are either in the form of a solution or in suspension form before being added to the cement.
• the spreading at 5 minutes of a mortar comprising an Optima 203 subjected to grinding at 100 ° C. in the absence of a sacrificial molecule is 205 mm, whereas it is 250 mm in the presence of 20% of methyl gallate in solution with the dispersant, or of 230 mm in the presence of 20% of methyl gallate suspended with the dispersant.
• the spreading at 5 minutes of a mortar comprising an Optima 203 subjected to grinding at 100 ° C. in the presence of 20% of methyl gallate, the dispersant and the sacrificial molecule being added separately to the cement, is 200 mm, value very close to the 205 mm of mortar ground without sacrificial molecule.
• Example 4 Validation of the Effect of Sacrificial Molecules on the Decrease in the Fluidizing Power of Various Dispersants Prepared by Copolymerization During the Manufacture of Cements During their Grinding
• the copolymer 1 containing the sacrificial molecule TAA-OL is prepared from the following reagents:
• Methoxy polyethylene glycol methacrylate (MMPEG1 100) (Supplier: Aldrich): 19.7 g
• antioxidant monomer 2, 2, 6, 6-tetramethyl-4-piperidinyl methacrylate (TAA-OL) (Supplier: Evonik Industries): 1, 7 g
• the procedure for manufacturing the tested PCP is as follows:
• copolymers 2 to 5 are prepared according to the same procedure by replacing the TAA-OL with the monomer to be tested according to the molar percentages shown in Table 6: Table 6: Composition of the copolymers containing the antioxidant in the polymer chain.
• Table 7 below presents the results of spreading tests carried out with different dispersing copolymers.
• the copolymer used according to the invention comprising at least one monomer with an antioxidant unit is either added during the grinding of a clinker or is added to a mortar (control).
• Table 7 Summary of the spreading tests carried out during the grinding at 100 ° C. of a clinker in comparison with a control corresponding to the addition of the composition according to the invention to a mortar

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Structural Engineering (AREA)
• Materials Engineering (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Curing Cements, Concrete, And Artificial Stone (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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