Early strength enhancement of cements

Abstract

A method of making a cement composition, comprising grinding a cement clinker and a strength-enhancing agent, thereby producing a hydraulic cementitious powder, wherein the strength-enhancing agent is present in the hydraulic cementitious powder in an amount of from 0.001% to 0.09% based on dry weight of the hydraulic cementitious powder. The strength-enhancing agent is a compound represented by the following structural formula (I). The definitions of variables R1, R2, and R3 as well as R10, R20, and R30 are provided herein.

1 . A method of making a cement composition, comprising:
 grinding a cement clinker and a strength-enhancing agent, thereby producing a hydraulic cementitious powder,   
       wherein:
 the strength-enhancing agent is present in the hydraulic cementitious powder in an amount of from 0.001% to 0.09% based on dry weight of the hydraulic cementitious powder, 
 the strength-enhancing agent is a compound represented by the following structural formula: 
 
       
         
           
           
               
               
           
         
         wherein:
 R 1  is (C 1 -C 4 )alkyl-OH; and 
 R 2  and R 3 , each independently, is (C 0 -C 3 )alkyl-COOR*, wherein R* is H, Na + , K + , or ½ Ca ++ . 
 
       
     
     
         2 . The method of  claim 1 , further including adding to the cement clinker at least one supplemental cementitious material selected from the group consisting of: fly ash, granulated blast furnace slag, limestone, calcined clay, natural pozzolan and artificial pozzolan. 
     
     
         3 . The method of  claim 1 , wherein the cement clinker includes C 3 A in an amount of 0.3% to 9.0% based on dry weight of cement clinker. 
     
     
         4 . The method of  claim 1 , further comprising grinding with the strength enhancement agent and the cement clinker at least one supplemental component selected from a grinding aid, a set retarding agent, or a set accelerating agent. 
     
     
         5 . The method of  claim 1 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid, and further wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder, and   the at least one grinding aid is added in the amount of from 0.001% to 0.06% based on dry weight of the hydraulic cementitious powder.   
     
     
         6 . The method of  claim 1 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid and a set retarding agent, wherein:
 the strength enhancement agent is present in the amount of 0.001-0.03% based on dry weight of the hydraulic cementitious powder;   the at least one grinding aid is added in the amount of from 0.001% to 0.06% based on dry weight of the hydraulic cementitious powder;   the set retarding agent is added in the amount of 0.001-0.03% based on dry weight of the hydraulic cementitious powder.   
     
     
         7 . The method of  claim 1 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid and a set accelerating agent, wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder,   the at least one grinding aid is added in the amount of from 0.001 to 0.06% based on dry weight of the hydraulic cementitious powder,   the set accelerating agent is added in the amount of from 0.001% to 0.2% based on dry weight of the hydraulic cementitious powder.   
     
     
         8 . The method of  claim 1 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid, a set retarding agent, and a set accelerating agent, wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder,   the at least one grinding aid is added in the amount of from 0.001% to 0.06% based on dry weight of the hydraulic cementitious powder,   the set retarding agent is added in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder, and   the set accelerating agent is added in the amount of 0.001% to 0.2% based on dry weight of the hydraulic cementitious powder.   
     
     
         9 . The method of  claim 5 , wherein the grinding aid is one or more of a glycol, glycerin, alkanolamine, acetic acid or an acetic acid salt. 
     
     
         10 . The method of  claim 6 , wherein the set retarding agent is one or more of a gluconate salt, a molasses, sucrose, or a corn syrup. 
     
     
         11 . The method of  claim 7 , wherein the set accelerating agent is one or more of a thiocyanate salt or a chloride salt. 
     
     
         12 . (canceled) 
     
     
         13 . The method of  claim 4  wherein the strength enhancing agent is EDG or a salt thereof, the grinding aid is the glycol, the set retarding agent is sodium gluconate, and the set accelerating agent is sodium thiocyanate. 
     
     
         14 . The method of  claim 1 , further including grinding the cement clinker and the strength-enhancing agent with an alkali sulfate. 
     
     
         15 . The method of  claim 1 , wherein the content of Na 2 O equivalent in the hydraulic cementitious material is less than or equal to 0.7% by weight of the hydraulic cementitious powder. 
     
     
         16 . A composition prepared by the method of  claim 1 . 
     
     
         17 . An additive composition, comprising:
 (A) a strength-enhancing agent represented by the following structural formula:   
       
         
           
           
               
               
           
         
         wherein:
 R 1  is a (C 1 -C 4 )alkyl-OH; and 
 R 2  and R 3 , each independently, is a (C 0 -C 3 )alkyl-COOR*, wherein 
 
         R* is H, Na + , K + , or ½ Ca ++ ; 
       
       and
 (B) at least one grinding aid selected from one or more of a glycol, glycerin, or acetic acid or an acetic acid salt, 
 wherein the additive composition is a liquid. 
 
     
     
         18 . The additive composition of  claim 17 , wherein the weight ratio of the strength enhancing agent to the grinding aid is from 1:9 to 9:1. 
     
     
         19 . The additive composition of  claim 17 , further comprising a set retarding agent, a set accelerating agent, or a mixture thereof. 
     
     
         20 . The additive composition of  claim 17 , wherein the strength enhancing agent is N-(2-hydroxyethyl)iminodiacetic acid (EDG) or a salt thereof. 
     
     
         21 . The additive composition of  claim 17 , wherein the at least one grinding aid is diethylene glycol. 
     
     
         22 . The additive composition of  claim 17 , further comprising sodium gluconate or sodium thiocyanate. 
     
     
         23 . The additive composition of  claim 17 , further comprising an alkali sulfate. 
     
     
         24 . A cementitious composition comprising a cementitious binder obtained by grinding a cement clinker with the additive composition of  claim 17 . 
     
     
         25 . A cement composition, comprising:
 a hydraulic cementitious powder;   a strength-enhancing agent, said strength-enhancing agent being present in an amount of from 0.001% to 0.09% based on dry weight of the hydraulic cementitious powder,   wherein the strength-enhancing agent is a compound represented by the following structural formula:   
       
         
           
           
               
               
           
         
         wherein:
 R 1  is a (C 1 -C 4 )alkyl-OH; and 
 R 2  and R 3 , each independently, is a (C 0 -C 3 )alkyl-COOR*, wherein 
 
         R* is H, Na + , K + , or ½ Ca ++ ; and 
         at least one grinding aid selected from a glycol, glycerin, or acetic acid or an acetic acid salt. 
       
     
     
         26 . An additive composition for use in grinding with a cement clinker, said composition comprising:
 (A) a strength-enhancing agent represented by the following structural formula:   
       
         
           
           
               
               
           
         
         wherein:
 R 1  is a (C 1 -C 4 )alkyl-OH; and 
 R 2  and R 3 , each independently, is a (C 0 -C 3 )alkyl-COOR*, wherein 
 
         R* is H, Na + , K + , or ½ Ca ++ ; and 
         (B) at least one grinding aid selected from one or more of a glycol, glycerin, or acetic acid or a salt thereof, 
         wherein the additive composition is a liquid. 
       
     
     
         27 . A mixture of a cement clinker and the additive composition of  claim 17 . 
     
     
         28 . A method of  claim 1 , wherein the strength-enhancing agent is made by a process comprising:
 reacting a monohaloacetic acid chosen from monochloroacetic acid and monobromoacetic acid, or a salt thereof, with a alkanolamine chosen from ethanolamine, isopropanolamine, and isobutanolamine under alkaline conditions to generate the strength-enhancing agent represented by the structural formula   
       
         
           
           
               
               
           
         
         wherein: 
         R 1  is (C 1 -C 4 )alkyl-OH; 
         R 2  and R 3 , each independently, represent —CH 2 COO − R*, and R* is H, Na + , K + , or ½ Ca ++ . 
       
     
     
         29 . The method of  claim 28 , wherein the haloacetic acid or its salt is chloroacetic acid or its salt, and R 1  is —CH 2 CH 2 OH. 
     
     
         30 . A method for making a strength-enhancing agent, comprising:
 reacting a haloacetic acid chosen from one or more of a chloroacetic acid and a bromoacetic acid, or a salt thereof, with one or more alkanolamines of the structural formula (I)   
       
         
           
           
               
               
           
         
         under alkaline conditions, to generate the strength-enhancing agent represented by structural formula (II) 
       
       
         
           
           
               
               
           
         
         wherein:
 each R 10  is independently chosen from H, (C 1 -C 4 )alkyl-OH, provided that in structural formula (I) at least one group R 10  is not H; 
 R 20  is chosen from (C 1 -C 4 )alkyl-OH, and —C(R 4 ) 2 COO − M + ; and 
 R 30  is —C(R 4 ) 2 COO − M + ; 
 each R 4  is independently chosen from hydrogen, Br, and Cl; and 
 M +  is H + , Na + , K + , or ½ Ca ++ . 
 
       
     
     
         31 . The method of  claim 30 , wherein:
 the chloroacetic acid is monochloracetic acid or a salt thereof;   the compound represented by structural formula (I) is ethanolamine represented by the following structural formula HO—CH 2 —CH 2 —NH 2 ; and   the strength-enhancing agent represented by structural formula (II) is sodium ethanol-diglycine   
       
         
           
           
               
               
           
         
       
       wherein the monochloracetic acid or a salt thereof and the ethanolamine are reacted in the presence of sodium hydroxide at above room temperature. 
     
     
         32 . A strength-enhancing agent made by the methods according to  claim 28 . 
     
     
         33 . An additive composition, comprising:
 a first component; and   a cement additive component   
       wherein:
 the cement additive component is one or more agents chosen from a glycol, glycerol, acetic acid or a salt thereof, an alkanolamine, an amine, a carbohydrate, a water-reducing additive, an air-entraining agent, a chloride salt, a nitrite salt, a nitrate salt, and a thiocyanate salt; and 
 the first component is prepared by reacting a haloacetic acid chosen from one or more of a chloroacetic acid and a bromoacetic acid, or a salt thereof, with one or more alkanolamines of the structural formula (I) 
 
       
         
           
           
               
               
           
         
       
       under alkaline conditions, to generate the first component represented by structural formula (II) 
       
         
           
           
               
               
           
         
       
       wherein:
 each R 10  is independently chosen from H, (C 1 -C 4 )alkyl-OH, provided that in structural formula (I) at least one group R 10  is not H; 
 R 20  is chosen from (C 1 -C 4 )alkyl-OH, and —C(R 4 ) 2 COO − M + ; and 
 R 30  is —C(R 4 ) 2 COO − M + ; 
 each R 4  is independently chosen from hydrogen, Br, and Cl; and 
 M +  is H + , Na + , ½ Ca ++ . 
 
     
     
         34 . The additive composition of  claim 33 , wherein:
 the chloroacetic acid is monochloracetic acid or a salt thereof;   the compound represented by structural formula (I) is ethanolamine represented by the following structural formula HO—CH 2 —CH 2 —NH 2 ; and   the strength-enhancing agent represented by structural formula (II) is sodium ethanol-diglycine   
       
         
           
           
               
               
           
         
         wherein the monochloracetic acid or a salt thereof and the ethanolamine are reacted in the presence of sodium hydroxide at above room temperature. 
       
     
     
         35 . The additive composition of  claim 33 , wherein the additive composition is in liquid form. 
     
     
         36 . A concrete composition, comprising:
 the additive composition of  claim 33 ,   cement;   a fine aggregate;   a coarse aggregate, and   at least one supplemental cementitious material chosen from fly ash, granulated blast furnace slag, limestone, calcined clay, natural pozzolan, and artificial pozzolan.   
     
     
         37 . A method of making a cement composition, comprising:
 reacting a monohaloacetic acid chosen from monochloroacetic acid and monobromoacetic acid, or a salt thereof, with a alkanolamine chosen from ethanolamine, isopropanolamine, and isobutanolamine under alkaline conditions to generate the strength-enhancing agent represented by the structural formula   
       
         
           
           
               
               
           
         
         wherein: 
         R 1  is (C 1 -C 4 )alkyl-OH; and 
         R 2  and R 3 , each independently, represent —CH 2 COO − R*, wherein R* is H, Na + , K + , or ½ Ca ++   
       
       thereby preparing a reaction mixture;
 adding the reaction mixture without purification to a cement clinker; and 
 grinding the cement clinker and the reaction mixture, thereby producing a hydraulic cementitious powder. 
 
     
     
         38 . The method of  claim 4 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid, and further wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder, and   the at least one grinding aid is added in the amount of from 0.001% to 0.1% based on dry weight of the hydraulic cementitious powder.   
     
     
         39 . The method of  claim 4 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid and a set retarding agent, wherein:
 the strength enhancement agent is present in the amount of 0.001-0.03% based on dry weight of the hydraulic cementitious powder;   the at least one grinding aid is added in the amount of from 0.001% to 0.1% based on dry weight of the hydraulic cementitious powder;   the set retarding agent is added in the amount of 0.001-0.03% based on dry weight of the hydraulic cementitious powder.   
     
     
         40 . The method of  claim 4 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid and a set accelerating agent, wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder,   the at least one grinding aid is added in the amount of from 0.001 to 0.1% based on dry weight of the hydraulic cementitious powder,   the set accelerating agent is added in the amount of from 0.001% to 0.2% based on dry weight of the hydraulic cementitious powder.   
     
     
         41 . The method of  claim 4 , further comprising grinding with the strength enhancement agent and the cement clinker at least one grinding aid, a set retarding agent, and a set accelerating agent, wherein:
 the strength enhancement agent is present in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder,   the at least one grinding aid is added in the amount of from 0.001% to 0.1% based on dry weight of the hydraulic cementitious powder,   the set retarding agent is added in the amount of from 0.001% to 0.03% based on dry weight of the hydraulic cementitious powder, and   the set accelerating agent is added in the amount of 0.001% to 0.2% based on dry weight of the hydraulic cementitious powder.   
     
     
         42 . The method of  claim 1 , further including grinding the cement clinker and the strength-enhancing agent with an alkali sulfate and/or an alkali carbonate. 
     
     
         43 . (canceled) 
     
     
         44 . (canceled) 
     
     
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         52 . (canceled)