HK40019843A - Method for controlling clay impurities in construction aggregates and cementitious compositions - Google Patents

Description

Method for controlling clay impurities in construction aggregates and cementitious compositions

Technical Field

The present invention relates to treating sand aggregates used in the manufacture of building materials, and more particularly to clay in mitigation (mitigation) building aggregates using low chloride cationic polymers as described in further detail.

Background

Because clay materials are present in sand, crushed rock or gravel and other aggregates commonly used in construction applications, they are often present in construction materials such as concrete, mortar, asphalt, road base and oil and gas well drilling muds (used to consolidate the annular space between a pipe and a wellbore). Due to the lamellar structure, the clay can absorb water and chemical agents, so that the performance of the building material is reduced. A common method of mitigating the deleterious effects of clays is to wash them off of the aggregates. However, beneficial fines are also removed during the washing process.

It is known to use quaternary amine compounds to alter the properties or characteristics of clays. For example, in U.S. patent nos. 6,352,952 and 6,670,415 (to w.r. Grace & co. -Conn.), Jardine et al disclose that quaternary amines can be used to minimize the adverse effects of clays on the dosing efficiency of superplasticizers (superplastizers) used in concrete made using sand aggregates containing such clays.

As another example, in us patent 8,257,490 and us patent 8,834,626 assigned to Lafarge s.a., Jacquet et al disclose compositions for "inerting" clay in aggregate that include quaternary amine functionality, such as diallyldialkylammonium, quaternized (meth) acrylates of dialkylaminoalkyl groups, and quaternized dialkylaminoalkyl N-substituted (meth) acrylamides. Among these groups are cationic polymers obtained by polycondensation of dimethylamine and epichlorohydrin. Similar compositions are disclosed by Brocas in world intellectual property organization application (publication No. 2010/112784a 1), also assigned to Lafarge s.a.

It is an object of the present invention to mitigate the deleterious effects of clays while leaving beneficial fines behind. It is another object of the present invention to mitigate the deleterious effects of clays while improving the properties of building materials. Advantages of the present invention include improved mortar and concrete properties (including workability, strength), asphalt properties (e.g., binder requirements), and road base properties (e.g., improved flowability). Washing can be reduced or eliminated, thereby leaving a greater content of beneficial fines (i.e., small aggregates) in the building material.

Additional benefits may also be realized for clay stabilization to reduce water loss in oil and gas well applications (involving fracturing a formation).

Summary of The Invention

The present invention relates to clay mitigation (clay-mitigation) methods and compositions believed to be useful for modifying clays carried or otherwise mixed within inorganic particulates such as sand aggregates, crushed stones (gravel, rock, etc.), granulated slag, and other inorganic particulate materials useful in building materials.

The clay harm reducing agents of the present invention can be incorporated into clay-containing building aggregates and materials such as mortar, concrete, asphalt, road base or drilling fluids and muds. The clay harm reducing agent can be incorporated into dry or wet aggregates.

In the case of hydratable cementitious compositions, the clay mitigation methods and compositions of the present invention can provide improved processability without increasing water demand; in the case of treating or washing aggregates, the composition of the invention may reduce the effort required to wash and/or dispose of the clay contained in the aggregates.

The methods and compositions of the present invention involve the use of low chlorine cationic polymers as described below.

An exemplary clay mitigation method of the present invention comprises: an ion-exchange polycondensate of dialkylamine and epichlorohydrin of the formula [ I ] is combined with a plurality of clay-containing aggregates,

wherein R is¹And R²Each independently represents a C1 to C3 alkyl group; and A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99% (more preferably 60-95%, most preferably 70-90%); and further wherein A^-Comprising based on A^-Represents a molar concentration of anionic groups of from 1 to 49% (more preferably from 5 to 40%, most preferably from 10 to 30%) of chloride ion groups.

The present invention also provides an admixture composition comprising the above-described low-chloride cationic polymer for treating clay-containing aggregate and at least one conventional chemical admixture for modifying hydratable mortar or concrete, such as one or more water-reducing admixtures (e.g., polycarboxylic acid-based comb polymer superplasticizers) or other conventional admixtures, as described in further detail below.

The exemplary admixture composition of the present invention may be introduced into the clay-containing aggregate at or after the quarry or at or after processing at the aggregate mine, or at a concrete mixing plant where the aggregate is combined with cement to provide a mortar or concrete composition. They may also be incorporated into crushed stone or rock contaminated with clay, such as crushed gravel or rock from quarries, prepared for road base or other construction uses (e.g., foundations) and other construction applications.

As described in more detail below, the above-described low chloride cationic polymers may also be used in other construction methods, such as in drilling applications, such as servicing a wellbore with a wellbore servicing fluid, e.g., a drilling (mud) fluid, a mud displacement fluid (mud displacement fluid), and/or a cementing composition, to inhibit swelling of a argillaceous (shale or clay) formation penetrated by the wellbore.

Further advantages and benefits of the present invention are described in more detail below.

Detailed description of the preferred embodiments

The present invention relates to methods and compositions for treating clay contained in aggregates, such as sand, crushed rock, crushed gravel, drilling mud, and other clay-containing aggregates used in or as part of building materials. Exemplary compositions of the invention include aggregate compositions, road base and asphalt, as well as cementitious compositions containing aggregate, such as mortar and concrete.

The present invention relates to the treatment of all types of clay. The clay may include, but is not limited to, swelling clays of the 2:1 type (e.g., montmorillonite-type clays) or the 1:1 type (e.g., kaolinites) or the 2:1:1 type (e.g., chlorites). The term "clay" refers to aluminum and/or magnesium silicates, including phyllosilicates having a lamellar structure; however, as used herein, the term "clay" may also refer to clays that do not have such a structure, such as amorphous clays. The invention is also not limited to clays that absorb polyoxyalkylene superplasticizers, such as those containing ethylene oxide ("EO") and/or propylene oxide ("PO") groups, but also clays that directly affect the properties of the building materials, whether in their wet or hardened state. Clays common in sands include, for example, montmorillonite, illite, kaolinite, muscovite, and chlorite. These are also included in the methods and compositions of the present invention.

The clay-containing sand and/or crushed rock or gravel treated by the method of the invention may be used in hydratable or non-hydratable cementitious materials, and such cementitious materials include mortars, concretes and asphalts that may be used in structural construction and construction applications, roads, foundations, civil engineering applications, as well as precast and precast applications.

The term "sand" as used herein shall mean aggregate particles typically used in building materials such as concrete, mortar and asphalt, and this typically relates to particles having an average particle size of between 0 and 8 mm (e.g. excluding 0), more preferably between 2 and 6 mm. The sand aggregate may comprise a calcareous, siliceous or siliceous limestone mineral. Such sands may be natural sands (e.g., from glaciers, alluvial or marine sediments, which are typically weathered to impart a smooth surface to the particles) or may be of the "manufactured" type made using mechanical crushers or grinding devices.

The term "cement" as used herein includes hydratable cements and portland cements made by comminuting clinker composed of hydraulic calcium silicates and one or more forms of calcium sulfate (e.g., gypsum) as an interground additive. Typically, the portland cement is combined with one or more supplementary cementitious materials (cementious materials), such as portland cement, fly ash, granulated blast furnace slag, limestone, natural pozzolans, or mixtures thereof, and provided as an admixture. The term "cementitious" refers to a material comprising portland cement or otherwise acting as a binder to bind together fine aggregates (e.g., sand), coarse aggregates (e.g., crushed stone, rock, gravel), or mixtures thereof.

The term "hydratable" is intended to mean a cement or cementitious material that hardens by chemical interaction with water. Portland cement clinker is a partially sintered material consisting primarily of hydratable calcium silicates. The calcium silicate being essentially tricalcium silicate (3 CaO. SiO)₂In the cement chemical symbol "C₃S') and dicalcium silicate (2 CaO. SiO)₂，"C₂S "), the former being the predominant form, with a lesser amount of tricalcium aluminate (3 CaO · Al)₂O₃，"C₃A') and tetracalcium aluminoferrite (4 CaO. Al)₂O₃·Fe₂O₃，"C₄AF"）。 See, e.g. Dodson, Vance H., Concrete Admixtures(Van Nostrand Reinhold, New York NY 1990), page 1.

The term "concrete" is used herein generally to denote a hydratable cementitious mixture comprising water, cement, sand, typically coarse aggregate such as crushed stone, rock or gravel, and optionally chemical admixtures.

It is contemplated that one or more conventional chemical admixtures may be used in the methods and compositions of the present invention. These include, but are not limited to, water reducing agents (e.g., lignosulfonates, Naphthalene Sulfonate Formaldehyde Condensates (NSFC), Melamine Sulfonate Formaldehyde Condensates (MSFC), polycarboxylic comb polymers (containing alkylene oxide groups, such as "EO" and/or "PO" groups), gluconates, and the like); a retarder; a coagulant; defoaming agents; an air-entraining agent; a surfactant; and mixtures thereof.

Among the additives, EO-PO type polymers having ethylene oxide ("EO") and/or propylene oxide ("PO") groups and polycarboxylic acid-based groups are preferred. Cement dispersants contemplated for use in the methods and compositions of the present invention include EO-PO polymers and EO-PO comb polymers as described, for example, in U.S. Pat. Nos. 6,352,952B 1 and 6,670,415B 2 to Jardine et al, which refers to the polymers taught in U.S. Pat. No. 5,393,343 (assigned to the common assignee). These polymers are available under the trade name ADVA from GCP Applied Technologies Inc., Massachusetts, USA. Another exemplary cement dispersant polymer, also containing EO/PO groups, is obtained by polymerization of maleic anhydride and an ethylenically polymerizable polyalkene, as taught in U.S. Pat. No. 4,471,100. In addition, cement dispersant polymers containing EO/PO groups are taught in U.S. Pat. No. 5,661,206 and U.S. Pat. No. 6,569,234. The amount of such polycarboxylic acid cement dispersant used in the concrete may be in accordance with conventional amounts (e.g. 0.05% to 0.25% based on the weight of active polymer/weight of cementitious material).

Thus, the present exemplary admixture composition comprises at least one chemical admixture, such as one or more polycarboxylic acid-based cement dispersants, which are preferably polycarboxylic acid-based comb polymers having EO and/or PO groups, in combination with a low-chlorine cationic polymer, as described herein.

In a first exemplary embodiment, the present invention is a method of controlling clay impurities in building aggregates comprising: an ion-exchange polycondensate of dialkylamine and epichlorohydrin of the formula [ I ] is combined with a plurality of clay-containing aggregates,

wherein R is¹And R²Each independently represents a C1 to C3 alkyl group; and A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99%; and further wherein A^-Comprising based on A^-Chloride ion groups in an amount of 1 to 49% by molar concentration of the represented anionic groups.

In the second exemplary embodimentIn one embodiment, the present invention is a method based on the first example above, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 60 to 95%; and further wherein A^-Comprising based on A^-Chloride ion groups in an amount of 5 to 40% by molar concentration of the represented anionic groups.

In a third exemplary embodiment, the present invention is a method based on the first example described above, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 70-90%; and further wherein A^-Comprising based on A^-Chloride ion groups in an amount of 10 to 30% by molar concentration of the represented anionic groups.

In a fourth exemplary embodiment, the present invention is a method based on any one of the first to third examples described above, wherein R¹And R²Each independently represents a methyl group.

In a fifth exemplary embodiment, the present invention is a method based on any one of the first to fourth examples above, wherein the amount of the ion exchange polycondensate of formula [ I ] is from 2 to 50% based on the dry weight of clay present in the clay-containing aggregate.

In a sixth exemplary embodiment, the present invention is based on the method of any one of the first to fifth examples above, wherein the amount of the ion exchange polycondensate of formula [ I ] is from 3 to 40% based on the dry weight of clay present in the clay-containing aggregate.

In a seventh exemplary embodiment, the present invention is a method based on any one of the first to sixth examples above, wherein the amount of the ion exchange polycondensate of formula [ I ] is from 4 to 30% based on the dry weight of clay present in the clay-containing aggregate.

In an eighth exemplary embodiment, the present invention is based on the method of any one of the first to seventh examples above, wherein the clay-containing aggregate is selected from fine aggregates (e.g., sand), coarse aggregates (e.g., gravel, stone), or mixtures thereof.

In a ninth exemplary embodiment, the present invention is based on the method of any one of the first to eighth examples above, wherein the ion-exchange polycondensate of formula [ I ] is introduced into the plurality of clay-containing aggregates before, during, or after combining the ion-exchange polycondensate with a cementitious binder.

In a tenth exemplary embodiment, the present invention is based on the method of any one of the first to ninth examples above, wherein the plurality of clay-containing aggregates and the ion-exchange condensation polymer of dialkylamine and epichlorohydrin are further combined with a hydratable cementitious binder and a polycarboxylic acid-based polymer water-reducing admixture.

In an eleventh exemplary embodiment, the present invention is based on the method of any one of the first to tenth examples above, wherein the plurality of clay-containing aggregates and the ion-exchange condensation polymer of dialkylamine and epichlorohydrin are further combined with a hydratable gelling binder and a water reducing agent selected from the group consisting of lignosulfonates, Naphthalene Sulfonate Formaldehyde Condensates (NSFCs), Melamine Sulfonate Formaldehyde Condensates (MSFCs), polycarboxylic acid-based comb polymers (containing alkylene oxide groups, such as "EO" and/or "PO" groups), gluconates, and the like; a retarder; a coagulant; defoaming agents; an air-entraining agent; a surfactant; and mixtures thereof.

In a twelfth exemplary embodiment, the present invention is an aggregate composition made by any of the methods described in any of the first through eleventh examples above.

In a thirteenth exemplary embodiment, the present invention is an admixture composition comprising:

an ion-exchange polycondensate of dialkylamine and epichlorohydrin of the formula

Wherein R is¹And R²Each independently represents a C1 to C3 alkyl group; and wherein A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99%; and further wherein A^-Comprising based on A^-In an amount of 1 to 49% by mole of the anionic groups representedA chloride ion group; and at least one chemical admixture (e.g., a water-reducing admixture) for modifying the properties of cement, mortar or concrete.

In a fourteenth exemplary embodiment, the present invention is the admixture composition according to the thirteenth exemplary embodiment, wherein the at least one water reducing agent for plasticizing cement, mortar or concrete is selected from the group consisting of water reducing agents (e.g., lignosulfonates, Naphthalene Sulfonate Formaldehyde Condensates (NSFCs), Melamine Sulfonate Formaldehyde Condensates (MSFCs), polycarboxylic acid-based comb polymers (containing alkylene oxide groups, such as "EO" and/or "PO" groups), gluconates, and the like); a retarder; a coagulant; defoaming agents; an air-entraining agent; a surfactant; and mixtures thereof.

In a fifteenth exemplary embodiment, the present invention is an admixture composition based on the thirteenth to fourteenth exemplary embodiments, the admixture composition comprising a polycarboxylic acid-based comb polymer water-reducing agent for concrete.

In a sixteenth exemplary embodiment, the present invention is an additive composition for treating a composition containing clay-containing aggregate (e.g., hydratable cementitious composition, dry or wet aggregate pile, asphalt, etc.) comprising an ion-exchanged condensation polymer of a dialkylamine of formula [ I ] and epichlorohydrin

Wherein R is¹And R²Each independently represents a C1 to C3 alkyl group; and wherein A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99%; and further wherein A^-Comprising based on A^-Chloride ion groups in an amount of 1 to 49% by molar concentration of the represented anionic groups; and at least one chemical admixture (e.g., a water-reducing admixture) for modifying the properties of cement, mortar or concrete.

For oil and gas well applications, the low chloride cationic polymers of the present invention may be introduced into an aqueous wellbore cement slurry or drilling fluid or mud to stabilize clay-containing formations.

As mentioned in the summary, the above-described low chloride cationic polymers may also be used in drilling applications such as wellbore mud drilling fluids and/or cementing compositions and methods of maintaining wellbores. Natural resources such as gas, oil and water present in a formation or region are typically recovered (recover) by drilling a wellbore down in the formation while circulating drilling fluid (also known as drilling mud) through the drill pipe and drill bit and up through the wellbore to the surface, as described in US 2007/0261849 to valenciano et al. The drilling fluid is used to lubricate the drill bit and carry the cuttings back to the surface. After the wellbore is drilled to the desired depth, the drill pipe and bit are typically removed from the wellbore while drilling fluid remains in the wellbore to provide hydrostatic pressure on the formation penetrated by the wellbore and thereby prevent formation fluid from flowing into the wellbore. Next, the drilling operation involves inserting a series of tubulars, such as casing, into the wellbore. Primary cementing is then typically performed whereby a cement slurry is pumped down the series of pipes and into the annulus between the series of pipes and the wellbore wall, thereby displacing the drilling mud, and the cement slurry sets into a hardened material (i.e., a sheath) and thereby seals the annulus.

The present inventors believe that the above-described low-chlorine cationic polymers are suitable for use as clay harm-reducing agents in aqueous drilling fluid (mud) compositions and/or well cementing compositions. Advantages or objectives of this include stabilizing argillaceous formations in the wellbore, such as shale and/or clay, which would otherwise be weakened and displaced by water in the aqueous wellbore mud. Due to the saturation and low permeability of shale formations, the penetration of a small amount of wellbore fluid into the formation can also cause a significant increase in the pore fluid pressure near the wellbore wall, thereby reducing effective cement support, which results in less stable wellbore conditions.

While the invention is described herein using a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention as otherwise described and claimed herein. There are modifications and variations to the described embodiments. More specifically, the following examples are given as specific illustrations of embodiments of the claimed invention. It should be understood that the invention is not limited to the specific details given in the examples. Unless otherwise specified, all parts and percentages in the examples and hereinafter of the specification are on a dry weight percent basis.

Example 1

Description of the materials:

An aqueous solution of epichlorohydrin and dimethylamine condensates (EPI-DMA, FL 2250) was obtained from SNF florerger, France. Ion chromatography measurements indicated that this 50% solution had a chloride concentration of 13.34%. The ion chromatography conditions were as follows: 10mM potassium hydroxide AS a mobile phase, an injection volume of 25 mL, a flow rate of 1 mL/min, a column temperature of 30 ℃, a Dionex. RTM. ICS-2100 system, a Dionex. RTM. Ionpac. AS19 analytical column, and a Dionex. RTM. Ionpac. AG19 guard column.

The polycondensate was then ion-exchanged for chloride with acetate ions. The resulting solution was then adjusted to 59% activity, which was described as a Clay Control Additive (CCA). The chloride content of this CCA solution was 3.07% as determined by ion chromatography. The% acetate of CCA was calculated as follows:

acetate% = 100 × (1- ((Cl% of CCA at 100% activity%)/(Cl% of EPI-DMA at 100%))

Based on these chloride concentrations, it was determined that the Clay Control Additive (CCA) contained 80% acetate and 20% chloride as counterions.

Example 2

This example illustrates the performance of a Clay Control Additive (CCA) in fine aggregate. Methylene Blue Value (MBV) testing was performed according to ASTM C1777-14. The MBV values were converted to sodium montmorillonite, described as% Mo-Meq, using an external calibration. The sand was then treated with CCA in two different doses described as% solids CCA/clay (% s/clay). Table 1 shows the results for six different sands.

It is apparent from table 1 that the Clay Control Additive (CCA) of the present invention exhibits excellent performance in reducing MBV values even at very low dosages.

Example 3

The efficacy of the Clay Control Additive (CCA) of the present invention was also evaluated in mortars using sands contaminated with different amounts of clay, measured according to the method described in example 1. The test was performed according to JIS a 5201 and the mixing design was composed of ordinary portland cement, slag, sand, and water at 300/690/1764/509 weight ratios. Polycarboxylic acid-based water-reducing admixtures commercially available from GCP Applied Technologies Inc., Cambridge, MA, USA) under the trade name MIRA 186 are also used in all mixtures. Mortar slump and flow were measured at the 3 minute, 2 hour and 4 hour marks and the results are summarized in table 2.

The results in table 2 clearly show that the Clay Control Additive (CCA) of the present invention mitigates the deleterious effects of clay and shows an increase in slump and flow for all three time intervals for all contaminated sands.

Example 4

The performance of the Clay Control Additive (CCA) of the present invention was also evaluated in concrete using a mixture of clean natural sand and artificial sand contaminated with clay of 0.96% Mo-Meg. The mixing design comprises 145 Kg/m³55 Kg/m of OPC cement³Fly ash, 66 Kg/m³Slag, 407 Kg/m³Natural sand, 515 Kg/m³Artificial sand, 312 Kg/m³711 Kg/m of stone of 10mm³190 Kg/m of stone of 20mm³Water and a water/cement ratio of 0.714. The polycarboxylic acid-based admixture was also used in a dosage of 0.086% solids/cement.

The mixing procedure was as follows: (1) mixing artificial sand with CCA for 1 minute; (2) adding natural sand and stone and mixing for 1 minute; (3) adding cement, fly ash and slag and mixing for 15 seconds; (4) add 80% water and mix for 2 minutes; (5) the polycarboxylic acid-based admixture and the remaining water were added and mixed for 3 minutes. After mixing, the slump, air content and 7-, 28-and 56-day compressive strength of the concrete were determined.

The results are shown in table 3.

As shown in table 3, the Clay Control Additive (CCA) of the present invention clearly exhibits a clay mitigation effect, as it provides an improvement in slump workability compared to the control, while maintaining other new mix-hardened concrete properties.

Example 5

This example demonstrates the performance of the Clay Control Additive (CCA) of the present invention in concrete using clean sand doped with various amounts of clay in the absence and presence of polycarboxylic acid-based superplasticizers. The concrete mix design is formulated as follows: 385 Kg/m³875 kg/m of cement³600 Kg/m of sand³400 Kg/m of 19 mm stone³9 mm stone and different amounts of water at various water/cement ratios.

Sodium montmorillonite (commercially available under the trade name POLARGEL @fromAmerican Colloid Company, Illinois, USA) was used as clay in all concrete mixtures and pre-hydrated to form a 5 wt% suspension in water. The weight of the dry sodium montmorillonite is used as a weight percentage of the sand, and the amount of the solid polycarboxylic acid superplasticizer is used as a weight percentage of the cement.

The concrete mixing procedure was as follows: (1) mixing the sand, stone and clay suspension for 30 seconds; (2) adding water and defoamer and mixing for 1 minute; (3) adding cement and mixing for 1 minute; (4) adding a polycarboxylic superplasticizer and mixing for 3 minutes if needed; (5) stopping the mixer and standing for 3 minutes; (6) mix for an additional 2 minutes. After mixing, slump was determined and the results are shown in table 4 below.

The results in table 4 clearly indicate the efficacy of the Clay Control Additive (CCA) of the present invention to mitigate the adverse effects of clay and restore slump workability. This property is significantly enhanced when a carboxylic acid based superplasticizer is used.

Example 6

In this example, the performance of the Clay Control Additive (CCA) of the present invention was evaluated in self-compacting concrete (SCC) in which a clean sand was doped with two levels of sodium montmorillonite clay. The mixing design is as follows: 445 Kg/m3 cement, 870 Kg/m3 sand, 530 Kg/m3 19 mm stone, 355 Kg/m3 mm stone and water. The amount of water was 183L/m 3 at 0.2% clay or 192L/m 3 at 0.4% clay to yield water/cement ratios of 0.41 and 0.43, respectively. The polycarboxylic superplasticizer is used in a dosage of 0.12% by weight solids/cement in all the mixtures. The mixing procedure was the same as described in example 4. Concrete flow (spreading) and compressive strength were measured and summarized in table 5.

The data in table 5 show that the Clay Control Additive (CCA) of the present invention inhibits the detrimental effects of clay and improves concrete flow workability with negligible effect on concrete strength.

The foregoing examples and embodiments are illustrative only and are not intended to limit the scope of the invention.

Claims (14)

1. A method of controlling clay impurities in building aggregates comprising: an ion-exchange polycondensate of dialkylamine and epichlorohydrin of the formula [ I ] is combined with a plurality of clay-containing aggregates,

wherein R is¹And R²Each independently represents a C1 to C3 alkyl group; and A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99%; and is

Further, wherein A^-ComprisesBased on A^-Chloride ion groups in an amount of 1 to 49% by molar concentration of the represented anionic groups.

2. The method of claim 1, wherein the amount of acetate is based on a^-The molar concentration of the represented anionic groups is 60-95%.

3. The method of any one of claims 1 to 2, wherein the amount of acetate is based on a^-The molar concentration of the represented anionic groups is 70-90%.

4. The method of any one of claims 1 to 3, wherein R¹And R²Each independently represents a methyl group.

5. The method of any of claims 1 to 4 wherein the amount of the ion exchange polycondensate of formula [ I ] is from 2 to 50% based on the dry weight of clay present in the clay-containing aggregate.

6. The method of any of claims 1 to 5 wherein the amount of the ion exchange polycondensate of formula [ I ] is from 3 to 40% based on the dry weight of clay present in the clay-containing aggregate.

7. The method of any of claims 1 to 6 wherein the amount of the ion exchange polycondensate of formula [ I ] is from 4 to 30% based on the dry weight of clay present in the clay-containing aggregate.

8. The method of any one of claims 1 to 7, wherein the clay-containing aggregate is selected from sand, gravel, crushed stone, or mixtures thereof.

9. The method of any one of claims 1 to 8, wherein the ion exchange polycondensate of formula [ I ] is introduced into the plurality of clay-containing aggregates before, during, or after combining the ion exchange polycondensate with a cementitious binder.

10. The method of any of claims 1 to 9, wherein the plurality of clay-containing aggregates and the ion-exchange condensation polymer of dialkylamine and epichlorohydrin are further combined with a hydratable cementitious binder and a polycarboxylic acid-based polymer water-reducing admixture.

11. The method of any of claims 1 to 10, wherein the plurality of clay-containing aggregates and the ion-exchanged condensation polymer of dialkylamine and epichlorohydrin are further combined with a hydratable cementitious binder and at least one chemical admixture selected from the group consisting of water reducers, set retarders, set accelerators, defoamers, air entraining agents, surfactants, and mixtures thereof.

12. The method of claim 11, wherein the at least one chemical admixture is a polycarboxylic acid comb polymer water reducer.

13. An aggregate composition made by the method of any one of claims 1 to 12.

14. An admixture composition comprising:

(A) ion-exchange polycondensates of dialkylamines of the formula [ I ] and epichlorohydrin

Wherein R is¹And R²Each independently represents C₁To C₃An alkyl group; and A is^-Represents an anionic group comprising acetate and chloride groups, wherein the amount of acetate is based on A^-A molar concentration of the represented anionic groups of 51-99%; and further wherein A^-Comprising based on A^-Chloride ion groups in an amount of 1 to 49% by molar concentration of the represented anionic groups; and

(B) at least one water reducing agent for plasticizing cement, mortar or concrete.