Use as an agent improving the workability of an aqueous formulation with a hydraulic binder base, of a (meth)acrylic comb-branched copolymer and an associative acrylic thickener

Abstract

The present invention pertains to the use, in the manufacture of an aqueous formulation with a hydraulic binder base, of a combination of at least one comb-branched copolymer having a (meth)acrylic skeleton, onto which are grafted side-chains terminated by a hydrophilic group, and at least one ASE acrylic polymer. This results in improving the workability of said formulation, without causing a segregation phenomenon.

1 . A method for improving workability of an aqueous formulation with a hydraulic binder base, the method comprising:
 adding to the aqueous formulation, an agent comprising:   a) at least one comb-branched (meth)acrylic copolymer having at least one side-chain bearing at least one alcoxy- or hydroxy-polyalkylene glycol hydrophilic group; and   b) at least one ASE acrylic polymer.   
     
     
         2 . The method of  claim 1 , wherein the comb-branched copolymer a) and the acrylic copolymer b) are added separately into the aqueous formulation. 
     
     
         3 . The method of  claim 1 , wherein the comb-branched copolymer a) and the acrylic copolymer b) are added in the form of a mixture. 
     
     
         4 . The method of  claim 3 , wherein the mixture has a dry solids content of between 10% and 50% of its total weight. 
     
     
         5 . The method of  claim 3 , wherein the mixture has a dry solids content of comb-branched copolymer a) of between 5% and 95% of its total solid matter. 
     
     
         6 . The method of  claim 1 , wherein the comb-branched copolymer a) comprises expressed as a percentage by weight of each of its monomers:
 a1) 5% to 30% of (meth)acrylic acid,   a2) 70% to 95% of at least one monomer having the of formula (I):   
       
         
           
           
               
               
           
         
         wherein:
 m, n, p, and q are whole numbers and m, n, and p are less than 150, q is greater than 0, and at least one whole numbers among m, n, and p is nonzero; 
 R is a radical comprising a polymerizable unsaturated function; 
 R 1  and R 2  are identical or different, and represent a hydrogen atom or an alkyl group. 
 R′ represents hydrogen, or a hydrocarbonated radical having 1 to 40 carbon atoms, or an ionic or ionizable group; 
 
         a3) 0% to 50% of at least one monomer different from monomers a1) and a2), 
         wherein a sum of percentages equals 100%. 
       
     
     
         7 . The method of  claim 1 , wherein the ASE acrylic polymer b) comprises (meth)acrylic acid and an ester of at least (meth)acrylic acid. 
     
     
         8 . The method of  claim 1 , wherein the comb-branched copolymer a) and the ASE acrylic polymer b) are obtained by radical polymerization in a solution, direct emulsion, or inverse emulsion, in a suspension or precipitation in a solvent, in the presence of at least one of a catalytic system and a transfer agent,
 by radical mediated polymerization,   by cobaloxyme mediated polymerization,   by atom transfer radical polymerization (ATRP),   by radical mediated polymerization by at least one sulfur derivative selected from the group consisting of a carbamate, a dithioester, a trithiocarbonate, and a xanthate.   
     
     
         9 . The method of  claim 1 , wherein the comb-branched copolymer a) and acrylic polymer b) have been distilled, after polymerization. 
     
     
         10 . The method of  claim 1 , wherein the comb-branched copolymer a) and acrylic polymer b) have been separated into several phases, by at least one static or dynamic separation process, by at least one polar solvents solvent. 
     
     
         11 . The method of  claim 1 , wherein the comb-branched copolymer a) and acrylic polymer b) are fully or partially neutralized by at least one neutralization agent having a monovalent or polyvalent cation. 
     
     
         12 . The method of  claim 1 , wherein the formulation is a cement, a mortar, a concrete, or a grout. 
     
     
         13 . The method of  claim 1 ,
 wherein the aqueous formulation with a hydraulic binder base comprises 0.1 % 2% solids content of components a) and b) in relation to a solid content of hydraulic binder.   
     
     
         14 . An aqueous formulation, comprising:
 a hydraulic binder base; and   an agent comprising:   a) at least one comb-branched (meth)acrylic copolymer having at least one side-chain bearing at least one alcoxy- or hydroxy-polyalkylene glycol hydrophilic group; and   b) at least one ASE acrylic polymer.   
     
     
         15 . An aqueous formulation of  claim 14 , wherein the comb-branched copolymer a) comprises, expressed as a percentage by weight of each of its monomers:
 a1) 5% to 30% of (meth)acrylic acid,   a2) 70% to 95% of at least one monomer having the of formula (I):   
       
         
           
           
               
               
           
         
         wherein:
 m, n, p, and q are whole numbers and m, n, and p are less than 150, q is greater than 0, and at least one whole numbers among m, n, and p is nonzero; 
 R is a radical comprising a polymerizable unsaturated function, 
 R 1  and R 2  are identical or different, and represent a hydrogen atom or an alkyl group, 
 R′ represents hydrogen or a hydrocarbonated radical having 1 to 40 carbon atoms, or an ionic or ionizable group, 
 
         a3) 0% to 50% of at least one monomer different from monomers a1) and a2), 
         wherein a sum of percentages equals 100%. 
       
     
     
         16 . The aqueous formulation of  claim 14 , wherein the ASE acrylic polymer b) comprises (meth)acrylic acid and an ester of a (meth)acrylic acid. 
     
     
         17 . The aqueous formulation of  claim 14 , wherein the comb-branched copolymer -a) and acrylic polymer b) are obtained by radical polymerization in a solution, direct emulsion, or inverse emulsion, in a suspension or precipitation in solvents, in the presence of catalytic at least one of a system and a transfer agent,
 by radical mediated polymerization,   by cobaloxyme mediated polymerization,   by atom transfer radical polymerization (ATRP), by radical mediated polymerization by at least one sulfur derivative selected from the group consisting of a carbamate, a dithioester, a trithiocarbonate, and a xanthate.   
     
     
         18 . The aqueous formulation of  claim 14 , wherein the comb-branched copolymer a) and acrylic polymer b) have been distilled, after polymerization. 
     
     
         19 . The aqueous formulation of  claim 14 , wherein the comb-branched copolymer a) and acrylic polymer b) have been separated into several phases, be at least one static or dynamic separation process, by at least one polar solvent. 
     
     
         20 . The aqueous formulation of  claim 14 , wherein the comb-branched copolymer a) and acrylic polymer b) are fully or partially neutralized by at least one neutralization agent having a monovalent or polyvalent cation. 
     
     
         21 . The aqueous formulation of  claim 14 , wherein the formulation is a cement, a mortar, a concrete, or a grout. 
     
     
         22 . An aqueous formulation of  claim 14 , comprising 0.1% to 2%, solids content of components a) and b) in relation to a solid content of the hydraulic binder.