Patent Grant
8623979
1. Field of Invention
The present invention relates to a cement dispersant and methods of making and using the same.
2. Description of Related Art
Cement dispersants are often added to cementitious compositions such as Portland cement, concrete other hydraulic cement compositions (hereinafter collectively “cement”) to improve the workability or slump properties of the cement, to reduce the amount of water necessary to obtain good workability, which improves the strength of the resulting cured cement. Dispersants, which are also sometimes referred to as fluidity modifiers or slump modifiers, also help control the hardening and curing time of the cement.
Cement disspersants have conventionally been based on polymers and copolymers of naphthalene, aminosulfonic acids and polycarboxylic acids. Although cement dispersants of this type do improve the workability of cement when used properly, slump loss still remains a persistent problem in the field. Unexpected delays in delivering cement to construction sites and/or changes in ambient temperatures can negatively impact the quality of the cement and decrease the slump. There exists a need for a cement dispersant that provides improves slump life properties and water reduction properties.
The present invention provides a dispersant for use in cementitious compositions that provides improved slump life properties and water reduction properties. The dispersant according to the invention comprises a copolymerization product of a first monomer (A) comprising a carboxylic acid such as, for example, acrylic acid, a second monomer (B) comprising an alkoxylated allyl alcohol sulfate such as, for example, an allyloxypolyethyleneglycol ammonium sulfate, and, optionally, a third monomer (C) comprising an alkoxylated allyl alcohol.
The present invention also provides: (1) a method of improving the slump properties of cement comprising dispersing into an admixture comprising cement and water a dispersant comprising a copolymerization product of a first monomer (A) comprising a carboxylic acid, a second monomer (B) comprising an alkoxylated allyl alcohol sulfate, and, optionally, a third monomer (C) comprising an alkoxylated allyl alcohol; (2) a method of forming a cement dispersaht comprising copolymerizing a first monomer (A) comprising a carboxylic acid, a second monomer (B) comprising an alkoxylated allyl alcohol sulfate, and, optionally, a third monomer (C) comprising an alkoxylated allyl alcohol to form a copolymerization product; and (3) a cement admixture comprising water, cement and a copolymerization product of a first monomer (A) comprising a carboxylic acid, a second monomer (B) comprising an alkoxylated allyl alcohol sulfate, and, optionally, a third monomer (C) comprising an alkoxylated allyl alcohol.
The foregoing and other features of the invention are hereinafter more fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.
The cement dispersant according to the present invention comprises a copolymerization product of a first monomer (A) comprising a carboxylic acid, a second monomer (B) comprising an alkoxylated allyl alcohol sulfate, and, optionally, a third monomer (C) comprising an alkoxylated allyl alcohol. The polymerization of the monomers into a copolymerization product is preferably accomplished using conventional solution, precipitation or emulsion polymerization techniques. Conventional polymerization initiators such as azo compounds, persulfates, peroxides, UV light, and the like may be used. Chain transfer agents such as alcohols (preferably isopropanol), amines, hypophosphites or mercapto compounds may be used to regulate or control-the molecular weight of the copolymerization product. The backbone of the copolymerization product preferably comprises a random combination of the repeat unit remaining after polymerization of the monomers. The resulting copolymerization product may be isolated by common isolation techniques including precipitation isolation and the like. If polymerization is carried out in water, the copolymerization product may simply be used in its aqueous solution.
The first monomer (A) used to form the copolymerization product according to the invention preferably comprises a carboxylic acid, amido carboxylic acid, C1-C6 alkyl ester of carboxylic acid, C1-C6 alkyl ester of amido carboxylic acid, hydroxylated C1-C6 alkyl ester of carboxylic acid, or a hydroxylated C1-C6 alkyl ester of amido carboxylic acid. Particularly preferred carboxylic acids for use as first monomer (A) include acrylic acid, methacrylic acid, acrylamide, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, and water-soluble salts thereof.
The second monomer (B) used to form the copolymerization product according to the invention preferably comprises an alkoxylated allyl alcohol sulfate according to Formula (I) below:
Where “R1” is (CH2—CH2—O)n, (CH2—CH(CH3)—O)n, or a mixture of both and “n” is an integer from about 1 to about 100; and “M” is sodium, potassium, calcium, ammonium or an organic amine such as triethylamine, morpholine, and the like. As noted in Formula (I) above, the second monomer (B) has a terminal sulfate group covalently bonded through an oxygen atom [—C—O—S—O3—], and thus is not a sulfonate, which has a terminal sulfate group covalently bonded directly to a carbon atom [—C—S—O3—]. Monomer (B) can be prepared by ethoxylation, propoxylation or a combination of the ethoxylation and propoxylation of an allyl alcohol followed by an addition of sulfamic acid, which produces the monomer unit having a covalently bonded sulfate terminated end group bonded through an oxygen atom.
The optional third monomer (C) used to form the copolymerization product according to the invention preferably comprises an alkoxylated allyl alcohol according to Formula (II) below:
Where “R2” is H or a lower (C1-C4) straight or branched alkyl chain; “R3” is CH2 or C═O; “R4” is (CH2—CH2—O)m, (CH2—CH(CH3)—O)m, or a mixture of both and “m” is an integer from about 1 to about 150; and “R5” is H or a C1-C18 straight or branched alkyl chain. Third monomer (C) is referred to as polyethylene gylcol allyl ether (PEGAE) when “R2” and “R5” are H; “R3” is CH2; and “R4” is (CH2—CH2—O). Third monomer (C) is referred to as polypropylene glycol allyl ether (PPGAE) when “R2” and “R5” are H; “R3” is CH2; and “R4” is (CH2—CH(CH3)—O). Third monomer (C) is referred to as polyethyleneglycollprbpylene glycol ally ether (PEGPGAE) when “R2” and “R5” are H; “R3” is CH2; and “R4” is (CH2—CH2—O—CH2—CH(CH3)—O). Third monomer (C) is referred to as hydroxyethyleneglycolmethylmethacrylate (HEME) when “R2” is CH3; “R3” is C═O; “R4” is (CH2—CH2—O); and “R5” is H. Third monomer (C) is referred to as methoxyethyleneglycolmethylmethacrylate (MHEM) when “R2” is CH3; “R3” is C═O; “R4” is (CH2—CH2—O); and “R5” is CH3. It will be appreciated that “R5” can be sulfonated.
Preferably, the molar ratio of first monomer (A) to second monomer (B) to third monomer (C) in the copolymerization product is in a range of from about 1 to about 10 for first monomer (A), from about 1 to about 4 for second monomer (B), and from about 0 or 1 to about 10 for third monomer (C). In other words, the molar ratio of first monomer (A) to second monomer (B) to third monomer (C) in the copolymerization product is from about 1-10:1-4:0 or 1-10. More preferably, the molar ratio of first monomer (A) to second monomer (B) to third monomer (C) in the copolymerization product is in a range of from about 2.5 to about 6 for first monomer (A), from about 1 to about 2 for second monomer (B), and from about 0 or 1 to about 3 for third monomer (C) (or about 2.5-6:1-2:0 or 1-3).
The dispersant according to the invention can be added to freshly mixed cement to disperse and to adjust the Theological properties of the admixture. As noted above, throughout the instant specification and in the appended claims, the term “cement” refers to all cementitious materials including, for example, Portland cement, concrete and other hydraulic cementitious compositions. The addition of the dispersant to freshly mixed cement compositions improves, for example, the slump life of the admixture and also reduces the amount Of water needed to obtain desired slump properties. Typically, the dispersant is added into an aqueous cement mixture in an amount in a range of about 0.1 percent by weight to about 1.0 percent by weight, and more preferably in an amount in a range of from about 0.2 percent by weight to about 0.32 percent by weight.
It will be appreciated that although the dispersant according to the invention is primarily intended for use in cement compositions, it can also be used in other compositions where dispersants are used. Examples include powdered inorganic and organic substances, for example clays, porcelain slips, silicate meals, chalk, carbon black, powdered rock, pigments, talc, synthetic material powders and hydraulic binding agents. Also, the dispersant can be used in the oilfield industry for oil well cementing. Additionally, the polymers can be used in the gypsum industry as dispersants or water reducing agents. Further, these polymers can be used to disperse SBR and NBR emulsion rubbers during polymerization and processing of the rubber. The dispersants according to the invention also find utility in other applications such as, for example, in metal pre-treatment and cooling and boiler water treatment applications.
The following examples are intended only to illustrate the invention and should not be construed as imposing limitations upon the claims. Unless specified otherwise, all reagents and equipment used in the following examples can be obtained from Sigma Aldrich, Inc. (St. Louis, Mo.) and/or Fisher Scientific International, Inc. (Hanover Park, IL). The allyloxypolyethyleneglycol ammonium sulfate monomers used in the examples are available from Bimax, Inc. (Cockeysville, Md.), and the allyloxypolyethyleneglycol/propylene glycol ammonium sulfate monomers used in the examples are available both from Bimax, Inc. and from Rhodia, Inc., (Cranbury, N.J.). The abbreviations shown in Table I below are used throughout the Examples:
Sample 1
A suitable flask was equipped with a condenser, an addition funnel, a mechanical stirrer, a thermometer and a nitrogen sparger. The flask was charged with 46.3 g (.075 mole @95%) of APES-10 and 90 g of deionized water. 16.2 g (0.225 mole @99%) of AA was charged to a 20 cc syringe and placed on a syringe pump. 9.12 g of a 16.6% solution of sodium persulfate (“initiator solution”) was charged to a separate syringe and placed on a separate syringe pump. The aqueous APES-10 solution was sparged with nitrogen and heated to 85° C. The AA and the initiator solution were pumped into to the aqueous APES-10 solution simultaneously over three hours. The resulting aqueous copolymer solution was heated for one more hour at 85° C. then cooled to room temperature. Caustic (50%) was then added to adjust the pH to 6.4. The resulting copolymerization product, acrylic acid/allyloxypolyethylene glycol sulfate ammonium salt (“AA/APES-10”), was in the form of a clear, light yellow solution. After diluting the solution to 25% solids by weight, a Brookfield viscosity of 31.7 cps was recorded. The physical properties for the AA/APES-10 copolymerization product were recorded in Table 2 below.
Samples 2-13
The same procedure and equipment used to produce Sample 1 was used to prepare the copolymerization products identified as Samples 2-13 in Table 2 below. The molar ratios of the monomers used to form the copolymerization products are also set forth in Table 2 below.
Sample 14
The same equipment used to produce Sample 1 was used to prepare an acrylic acid/allyloxypolyethyleneglycol sulfate ammonium salt/allyloxypolyethyleneglycol (AA/APES-10/PEGAE-10 terpolymer) copolymerization product. Specifically, 21.92 g (0.035 mole @95%) of APES-10 and 17.45 g (0.035 mole) of PEGAE-10 and 78.44 g of deionized water were charged to the flask. 15.14 g (0.21 mole) of AA was charged to a 20 cc syringe and placed on a syringe pump. 5.86 g of a 20% solution of sodium persulfate (“initiator solution”) was charged to a separate syringe and placed on a separate syringe pump. The aqueous APES-10/PEGAE-10 solution was sparged with nitrogen and heated to 85° C. The AA and the initiator solution were pumped into to the aqueous APES-10/PEGAE-10 solution simultaneously over three hours. The resulting aqueous terpolymer solution was heated for one more hour at 85° C. then cooled to room temperature. Caustic (50%) was then added to adjust the pH to 5.3. The resulting copolymerization product, acrylic acid/allyloxypolyethylene glycol sulfate ammonium salt/allyloxypolyethyleneglycol glycol (“AA/APES-10/PEGAE-10”), was in the form of a clear, light yellow solution. After diluting the solution to 25% solids by weight, a Brookfield viscosity of 31.5 cps was recorded. The physical properties for the AA/APES-10/PEGAE-10 copolymerization product were recorded in Table 2 below.
Samples 15-26
The same procedure and equipment used to produce Sample 14 was used to prepare the copolymerization products identified as Samples 15-26 in Table 2 below. The molar ratios of the monomers used to form the copolymerization products are also set forth in Table 2 below.
Several of the samples produced in Example 1 were subjected to 13-C NMR testing. The spectra were characterized by a broad polyacrylic acid type backbone. Strong resonances at 61, 70 and 72 ppm correspond to the polyethylene glycol moiety and a broad carbonyl region (179-184 ppm). A very low level (<3%) of unreacted allylic monomer was detected in some of the samples.
Each of the samples of dispersants produced in Example 1 was tested for slump efficacy using the Cement Mini-slump testing procedure known as the “Standard Test Method for Slump of Hydraulic Cement Concrete” ASTM C143-97, Vol. 04.02, which is hereby incorporated by reference in its entirety. Additional information regarding the Cement Mini-slump test is found in D. L. Kantro's, Influence of Water-Reducing Admixtures on Properties of Cement Paste—A Miniature Slump Test, Cement, Concrete and Aggregates, 2, (1980) pp. 95-102, the entire contents of which is hereby incorporated by reference. Specifically, 100 grams (g) of Type 1 Portland cement was added to a disposable beaker. 35 g water was added to the beaker and the cement and water was mixed for 30 seconds with a metal spatula to produce a slurry. 0.32 weight percent of each of the samples produced: in Example 1 was dosed via a disposable syringe into the cement slurry. The slurry was mixed for an additional 30 seconds. The cement slurry was poured into a mini-slump cone, which was sitting on a glass plate. The mini-slump cone was then filled to the top with the cement slurry and then the mini-slump cone was lifted quickly and evenly from the glass plate, allowing the cement slurry to flow onto the glass plate. The diameter of the cement slurry patty thus formed was measured. The measurement was the initial slump diameter. The material was returned to the disposable beaker, then re-mixed and measured every 30 minutes to monitor slump retention. The results of Mini-slump Testing using Samples 1-26 produced in Example 1 is shown in Table 3 below, where the term “Thick” means that the cement slurry thickened to such an extent that no meaningful slump data could be obtained.
Each of the samples of dispersants produced in Example 1 was tested for slump efficacy using the same procedure as in Example 2, except that 0.20 weight percent of each of the samples produced in Example 1 was dosed via a disposable syringe into the cement slurry. The results of Mini-slump Testing using Samples 1-26 produced in Example 1 is shown in Table 4 below.
To illustrate the relative efficacy of the dispersants produced in accordance with the invention with conventional dispersants, the Mini-slump Test was repeated using three different amounts of a conventional calcium naphthalene sulfonate condensate dispersant available from GEO Specialty Chemicals as DILOFLO® CA. The results of the comparative Mini-Slump Testing are shown in Table 5 below.
Comparative Example 4 demonstrates that nearly two times as much of a conventional cement dispersant must be used in order to achieve the same slump properties as can be obtained with cement dispersants according to the present invention.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative examples shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
This application is a divisional of commonly owned application Ser. No. 10/874,502, filed Jun. 23, 2004, now U.S. Pat. No. 7,271,214, which is a continuation-in-part of application Ser. No. 10/602,405, filed Jun. 23, 2003, now U.S. Pat. No. 6,869,998, all of which are hereby incorporated herein by reference for all purposes.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4457762 | Papalos et al. | Jul 1984 | A |
| 4457874 | Papalos et al. | Jul 1984 | A |
| 4479826 | Papalos et al. | Oct 1984 | A |
| 4652621 | Kadono et al. | Mar 1987 | A |
| 4674574 | Savoly et al. | Jun 1987 | A |
| 4711731 | Garvey et al. | Dec 1987 | A |
| 4741843 | Garvey et al. | May 1988 | A |
| 4744795 | Savoly et al. | May 1988 | A |
| 4814389 | Garvey et al. | Mar 1989 | A |
| 4870120 | Tsubakimoto et al. | Sep 1989 | A |
| 5158612 | Savoly et al. | Oct 1992 | A |
| 5180498 | Chen et al. | Jan 1993 | A |
| 5714001 | Savoly et al. | Feb 1998 | A |
| 5753744 | Darwin et al. | May 1998 | A |
| 5798425 | Albrecht et al. | Aug 1998 | A |
| 5866013 | Kessler et al. | Feb 1999 | A |
| 6140440 | Kinoshita et al. | Oct 2000 | A |
| 6174980 | Hirata et al. | Jan 2001 | B1 |
| 6176921 | Kinoshita et al. | Jan 2001 | B1 |
| 6239241 | Yamato et al. | May 2001 | B1 |
| 6264739 | Yamato et al. | Jul 2001 | B1 |
| 6444747 | Chen et al. | Sep 2002 | B1 |
| 6451881 | Vickers, Jr. et al. | Sep 2002 | B1 |
| 6454850 | Yamashita et al. | Sep 2002 | B2 |
| 6462014 | Johnson et al. | Oct 2002 | B1 |
| 6486260 | Yuasa et al. | Nov 2002 | B1 |
| 6548589 | Widmer et al. | Apr 2003 | B2 |
| 6673885 | Shibata et al. | Jan 2004 | B1 |
| 6727315 | Yamamoto et al. | Apr 2004 | B2 |
| 6864337 | Yuasa et al. | Mar 2005 | B2 |
| 6869998 | Bair et al. | Mar 2005 | B2 |
| 7271214 | Bair et al. | Sep 2007 | B2 |
| 20030052303 | Buentello et al. | Mar 2003 | A1 |
| Entry |
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| Supplementary European Search Report for EP 04755931 dated May 23, 2006, three pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20070270547 A1 | Nov 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10874502 | Jun 2004 | US |
| Child | 11835441 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10602405 | Jun 2003 | US |
| Child | 10874502 | US |
