Method for improving the mechanical strength, particularly the strength "at young ages" of cement matrices, and the cement matrices obtained thereby

Abstract

Cements or hydraulic binders may be prepared by adding an aqueous suspension comprising a ground mineral filler and at least one grinding aid agent to a cement or hydraulic binder. The resulting cement or hydraulic binder has very appreciably improved mechanical properties, particularly the property of “strength at young ages.” The grinding aid agent may be a natural or synthetic homopolymer and/or copolymer.

1 . A method of preparing a cement matrix or hydraulic binder, comprising: 
 adding an aqueous suspension comprising a ground mineral filler and at least one grinding aid agent to a cement or hydraulic binder.    
     
     
         2 . The method according to  claim 1 , wherein the grinding aid agent comprises at least one member selected from the group consisting of natural homopolymers, synthetic homopolymers, natural copolymers, synthetic copolymers and mixtures thereof.  
     
     
         3 . The method according to  claim 2 , wherein the grinding aid agent comprises synthetic homopolymers, copolymers or mixtures thereof prepared by polymerizing ethylenically unsaturated monomers, by polycondensation, or by ring opening polymerisation.  
     
     
         4 . The method according to  claim 1 , wherein the grinding aid agent comprises a polymer prepared by polymerizing at least one ethylenically unsaturated monomer, comprising at least one anionic monomer.  
     
     
         5 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one non-ionic monomer.  
     
     
         6 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one member selected from the group consisting of alkoxy-polyalkylene glycol ethylenic ester, aryloxy-polyalkylene glycol ethylenic ester, alkylaryloxy-polyalkylene glycol ethylenic ester, arylalkyloxy-polyalkylene glycol ethylenic ester, alkoxy-polyalkylene glycol ethylenic ether, aryloxy-polyalkylene glycol ethylenic ether, alkylaryloxy-polyalkylene glycol ethylenic ether, arylalkyloxy-polyalkylene glycol ethylenic ether, alkoxy-polyalkylene glycol ethylenic urethane monomer, aryloxy-polyalkylene glycol ethylenic urethane monomer, alkylaryloxy-polyalkylene glycol ethylenic urethane monomer, arylalkyloxy-polyalkylene glycol ethylenic urethane monomer, and mixtures thereof.  
     
     
         7 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one ethylenic monomer having at least two polymerizable double bonds.  
     
     
         8 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one cationic monomer.  
     
     
         9 . The method according to  claim 1 , wherein the grinding aid agent comprises a polymer prepared by polymerizing ethylenically unsaturated monomers comprising by weight: 
 a) 2% to 100% of at least one anionic monomer,    b) 0% to 50% of at least one non-ionic monomer,    c) 0% to 95% of at least one member selected from the group consisting of alkoxy-polyalkylene glycol ethylenic ester, aryloxy-polyalkylene glycol ethylenic ester, alkylaryloxy-polyalkylene glycol ethylenic ester, arylalkyloxy-polyalkylene glycol ethylenic ester, alkoxy-polyalkylene glycol ethylenic ether, aryloxy-polyalkylene glycol ethylenic ether, alkylaryloxy-polyalkylene glycol ethylenic ether, arylalkyloxy-polyalkylene glycol ethylenic ether, alkoxy-polyalkylene glycol ethylenic urethane monomer, aryloxy-polyalkylene glycol ethylenic urethane monomer, alkylaryloxy-polyalkylene glycol ethylenic urethane monomer, arylalkyloxy-polyalkylene glycol ethylenic urethane monomer, and mixtures thereof,    d) 0% to 3% of one or more ethylenic monomers having at least two polymerizable double bonds, and    e) 0% to 98% of at least one cationic monomer,    wherein the total of monomers a), b), c), d) and e) is equal to 100%.    
     
     
         10 . The method according to  claim 4 , wherein the ethylenically unsaturated monomer comprises at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic, crotonic, fumaric acid, maleic anhydride, isocrotonic acid, aconitic acid, mesaconic acid, sinapic acid, undecylenic acid, angelic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid, 2-methacrylamido-2-methyl-1-propane sulphonic acid, 3-methacrylamido-2-hydroxy-1-propane sulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzene sulphonic acid, methallyloxybenzene sulphonic acid, 2-hydroxy-3-(2-propenyloxy)propane sulphonic acid, 2-methyl-2-propene-1-sulphonic acid, ethylene sulphonic acid, propene sulphonic acid, 2-methyl propene sulphonic acid, styrene sulphonic acid, vinyl sulphonic acid, sodium methallylsulphonate, sulphoethyl acrylate, sulphopropyl acrylate, sulphoethyl methacrylate, sulphopropyl methacrylate, sulphomethacrylamide, sulphomethylmethacrylamide, alkylene glycol acrylate phosphate, alkylene glycol acrylate phosphonate, alkylene glycol acrylate sulphate, alkylene glycol acrylate sulphonate, alkylene glycol methacrylate phosphate, alkylene glycol methacrylate phosphonate, alkylene glycol methacrylate sulphate, alkylene glycol methacrylate sulphonate, vinyl phosphonate and mixtures thereof.  
     
     
         11 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one non-ionic monomer selected from the group consisting of acrylamide, methacrylamide, a derivative of acrylamide, a derivative of methacrylamide, C 1  to C 40  acrylic acid alkyl-esters, C 1  to C 40  methacrylic acid alkyl-esters, vinyl acetate, vinylpyrrolidone, styrene, α-methyl-styrene and mixtures thereof.  
     
     
         12 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one monomer selected from the group consisting of alkoxy-polyalkylene glycol ethylenic urethane monomer, aryloxy-polyalkylene glycol ethylenic urethane monomer, alkylaryloxy-polyalkylene glycol ethylenic urethane monomer, arylalkyloxy-polyalkylene glycol ethylenic urethane monomer, an alkoxy-polyalkylene glycol ethylenic ester monomer, aryloxy-polyalkylene glycol ethylenic ester monomer, alkylaryloxy-polyalkylene glycol ethylenic ester monomer, arylalkyloxy-polyalkylene glycol ethylenic ester monomer, an oxyalkylated, oxyarylated, oxyarylalkylated or oxyalkylarylated alkoxy-, aryloxy-, alkylaryloxy- or arylalkyloxy-acrylate or methacrylate or hemimaleate having an alkylene, arylene, alkylarylene or arylalkylene oxide number between 1 and 120; an alkoxy-polyalkylene glycol ethylenic ether monomer, aryloxy-polyalkylene glycol ethylenic ether monomer, alkylaryloxy-polyalkylene glycol ethylenic ether monomer, arylalkyloxy-polyalkylene glycol ethylenic ether monomer and mixtures thereof.  
     
     
         13 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one ethylenic monomer having at least two polymerizable double bonds which is selected from the group consisting of ethylene glycol dimethacrylate, divinylacetylene, divinylbenzene, trimethylolpropanetriacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurates, allyl ethers prepared from polyols and mixtures thereof.  
     
     
         14 . The method according to  claim 13 , wherein the polyols are selected from the group consisting of pentaerythritol, sorbitol, sucrose and mixtures thereof.  
     
     
         15 . The method according to  claim 4 , wherein said polymer is prepared by polymerizing at least two ethylenically unsaturated monomers comprising at least one anionic monomer and at least one cationic monomer selected from the group consisting of quarternized or unquarternized methacrylamido propyl trimethyl ammonium chloride or sulfate or the corresponding acrylates or acrylamides, quarternized or unquarternized trimethyl ammonium ethyl methacrylate chloride or sulfate or the corresponding acrylates or acrylamides, dimethyldiallyl ammonium chloride and mixtures thereof.  
     
     
         16 . The method according to  claim 4 , wherein the anionic monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid, 2-methacrylamido-2-methyl-1-propane sulphonic acid, 3-methacrylamido-2-hydroxy-1-propane sulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzene sulphonic acid, methallyloxybenzene sulphonic acid, 2-hydroxy-3-(2-propenyloxy)propane sulphonic acid, 2-methyl-2-propene-1-sulphonic acid, ethylene sulphonic acid, propene sulphonic acid, 2-methyl sulphonic acid, styrene sulphonic acid, vinyl sulphonic acid, sodium methallylsulphonate; sulphopropyl acrylate, sulphopropyl methacrylate, sulphomethylacrylamide, sulphomethylmethacrylamide, alkylene glycol acrylate phosphate, alkylene glycol acrylate phosphonate, alkylene glycol acrylate sulphate, alkylene glycol acrylate sulphonate, alkylene glycol methacrylate phosphate, alkylene glycol methacrylate phosphonate, alkylene glycol methacrylate sulphate, alkylene glycol methacrylate sulphonate, itaconic acid, maleic anhydride, sodium methallylsulphonate, styrene sulphonic acid and mixtures thereof.  
     
     
         17 . The method according to  claim 4 , wherein the anionic monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid, ethylene sulphonic acid, propene sulphonic acid, 2-methyl sulphonic acid, ethylene glycol methacrylate phosphate, a ethylene glycol acrylate phosphate and mixtures thereof.  
     
     
         18 . The method according to  claim 5 , wherein the non-ionic monomer is selected from the group consisting of ethyl acrylate, acrylamide and mixtures thereof.  
     
     
         19 . The method according to  claim 6 , wherein the alkoxy-, aryloxy-, alkylaryloxy- or arylalkyloxy-polyalkylene glycol ethylenic urethane monomer is selected from the group consisting of a) the reaction products of alkyloxy-polyalkylene glycol with a polymerizable unsaturated isocyanate; and b) the reaction products of methoxy-polyethylene glycol with an acrylic, methacrylic, vinyl or allyl isocyanate; 
 wherein the polyethylene glycol has a molecular weight greater than 300.    
     
     
         20 . The method according to  claim 6 , wherein the alkoxy-, aryloxy-, alkylaryloxy- or arylalkyloxy-polyalkylene glycol ethylenic ester monomer is selected from the group consisting of alkoxy-, aryloxy-, alkylaryloxy- or arylalkyloxy-polyalkylene glycol acrylates, methacrylates or hemialeates; oxyalkylated, oxyarylated, oxyarylalkylated or oxylalkylarylated alkoxy-, aryloxy-, alkylaryloxy- or arylalkyloxy-polyalkylene glycol acrylates, methacrylates or hemialeates having alkylene, arylene, alkylarylene or arylalkylene oxide numbers between 1 and 120; and alkyloxy-polyethylene glycol acrylates, methacrylates or hemialeates, wherein the polyethylene glycol has a molecular weight greater than 300.  
     
     
         21 . The method according to  claim 3 , wherein the grinding aid agent comprises a homopolymer of acrylic acid or methacrylic acid.  
     
     
         22 . The method according to  claim 3 , wherein the grinding aid agent comprises a homopolymer, a copolymer or a mixture of a homopolymer and a copolymer of at least one ethylenically unsaturated cationic monomer selected from the group consisting of quaternized or unquarternized methacrylamido propyl trimethyl ammonium chloride or sulfate or a corresponding acrylate or acrylamide, quaternized or not, quaternized or unquarternized trimethyl ammonium ethyl methacrylate chloride or sulfate or a corresponding acrylate or acrylamide, and dimethyldiallyl ammonium chloride.  
     
     
         23 . The method according to  claim 3 , wherein the polymers prepared by polycondensation or by ring opening polymerization are selected from the group consisting of polyaspartate, a derivative of polyaspartate, polylactates, water-soluble polyesters, polyamides, polylactones and mixtures thereof.  
     
     
         24 . The method according to  claim 3 , wherein the grinding aid agent is fractionated subsequent to polymerizing.  
     
     
         25 . The method according to  claim 2 , wherein the grinding aid agent has a completely acidic form.  
     
     
         26 . The method according to  claim 2 , wherein the grinding aid agent is partially or completely neutralized by one or more neutralization agents having a monovalent function or polyvalent function.  
     
     
         27 . The method according to  claim 26 , wherein the neutralization agent having a monovalent function is selected from the group consisting of compounds containing alkaline cations, primary aliphatic amines, secondary aliphatic amines, cyclic amines and mixtures thereof.  
     
     
         28 . The method according to  claim 27 , wherein the alkaline cations are selected from the group consisting of sodium, potassium, lithium, and ammonium, and 
 wherein the primary aliphatic amines, secondary aliphatic amines, cyclic amines and mixtures thereof are selected from the group consisting of ethanolamines, monoethylamine, diethylamine, cyclohexylamine and mixtures thereof.    
     
     
         29 . The method according to  claim 26 , wherein the neutralisation agent having a polyvalent function is selected from the group consisting of compounds containing divalent alkaline-earth cations, compounds containing trivalent cations, compounds containing cations having a valency higher than trivalent and mixtures thereof.  
     
     
         30 . The method according to  claim 29 , wherein the divalent alkaline-earth cations are selected from the group consisting of magnesium, calcium, and zinc, and 
 wherein the trivalent cation is aluminium.    
     
     
         31 . The method according to  claim 1 , wherein the mineral filler is selected from the group consisting of ultrafine fillers having a median diameter less than or equal to 20 μm measured with a Cilas™ 850 or Sedigraph™ 5100 type granulometer.  
     
     
         32 . The method—according to  claim 1 , wherein the mineral filler is selected from the group consisting of natural calcium carbonates, chalk, calcite, marble, limy rocks, precipitated calcium carbonate, barium carbonate, dolomite, talc, ground silica, silica, fumed silica, fumed titanium dioxide, diatomites, iron oxides, manganese oxides, titanium dioxide, chalk, kaolin, meta-kaolin, clays, mica, plasters, fly ash, slag, calcium sulphate, zeolites, basalt, barium sulphate, aluminium trihydroxide and mixtures thereof.  
     
     
         33 . The method according to  claim 1 , wherein the aqueous suspension has a concentration of dry matter ranging from 10% to 85% by weight.  
     
     
         34 . A cement matrix or a hydraulic binder, prepared by the method of  claim 1 .  
     
     
         35 . A cement matrix or hydraulic binder, prepared by the method of  claim 2 .  
     
     
         36 . A cement matrix or hydraulic binder, prepared by the method of  claim 4 .  
     
     
         37 . A cement matrix or hydraulic binder, prepared by the method of  claim 5 .  
     
     
         38 . A cement matrix or hydraulic binder, prepared by the method of  claim 7 .  
     
     
         39 . A cement matrix or hydraulic binder, prepared by the method of  claim 8 .  
     
     
         40 . A cement matrix or hydraulic binder, prepared by the method of  claim 9 .  
     
     
         41 . A cement matrix or hydraulic binder, prepared by the method of  claim 21 .  
     
     
         42 . A cement matrix or hydraulic binder, prepared by the method of  claim 22 .  
     
     
         43 . A cement matrix or hydraulic binder, prepared by the method of  claim 23 .  
     
     
         44 . A cement matrix or hydraulic binder, prepared by the method of  claim 24 .  
     
     
         45 . A cement matrix or hydraulic binder, prepared by the method of  claim 25 .  
     
     
         46 . A cement matrix or hydraulic binder, prepared by the method of  claim 26 .  
     
     
         47 . A cement matrix or hydraulic binder, prepared by the method of  claim 32 .  
     
     
         48 . A concrete, comprising 
 the cement matrix or hydraulic binder according to  claim 34 .    
     
     
         49 . A mortars comprising 
 the cement matrix or hydraulic binder according to  claim 34 .    
     
     
         50 . A hydraulic concrete, comprising: 
 the cement matrix or hydraulic binder according to  claim 34 .    
     
     
         51 . A grout, comprising: 
 the cement matrix or hydraulic binder according to  claim 34 .    
     
     
         52 . A composition based on cement and/or semihydrate calcium sulphate, comprising: 
 the cement matrix or hydraulic binder according to  claim 34 .    
     
     
         53 . A building, offshore construction, bridge petroleum cement or road, comprising: 
 the cement matrix or hydraulic binder according to  claim 34.