JP2002535232A - Sugar derivative composition for changing properties of cement and cementitious composition and method for producing the same - Google Patents

Abstract

(57) Abstract An exemplary composition comprises a plurality of particles to be dispersed (eg, calcium carbonate or a binder material, eg, Portland cement) and a compound for dispersing the plurality of particles. These compounds are linked by an amine, amide, imide, or urea group to a non-sugar substituent comprising one or more alkyl, aryl, alkylaryl, oxyalkylene, polyoxyalkylene groups, or mixtures thereof. Comprising a group of a sugar or a sugar derivative. Exemplary compounds for dispersing the particles and modifying the properties of the hydratable composition, such as a cementitious mixture (eg, concrete, mesonry, mortar, or cement), and for preparing these compounds and for preparing the particles and A method for modifying a containing composition is disclosed. These compounds and methods are useful in cement and cementitious compositions to enhance flow, strength and crush performance, or other properties. It is believed that the present invention also provides one or more of these properties in an aqueous environment (eg, a slurry) in which the particles, eg, cement particles, are dispersed.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention comprises one or more alkyl, aryl, alkylaryl, oxyalkylene, or polyoxyalkylene groups by amine, amide, imide, or urea groups, or mixtures thereof. It relates to the dispersion of particles using a compound comprising a sugar or sugar derivative group attached to a non-sugar substituent. The particles to be dispersed may be inorganic (eg, calcium carbonate) and include a hydratable cementitious binder, such as Portland cement. More particularly, the invention encompasses methods of making these compounds and methods of altering the properties of cementitious compositions.

[0002] Although flowable at elevated hydrated cement composition by introducing the background excess water of the invention may be obtained, resulting building or civil engineering structures are produced from cementitious mixtures desired It is generally known that they will have lower compressive strength or other disadvantaged properties, such as reduced resistance.

[0003] Various additives have been proposed to increase the flowability, or "slump," in cement compositions such as mortar and concrete, without increasing the water content of the initially produced composition. . Such additives or admixtures are chemically classified as "superplasticizers" or "water reducers" and include compounds such as, for example, naphthalene sulfonate formaldehyde condensates, lignin sulfonates, and the like.

A water-loss admixture is disclosed in US Pat. No. 5,393,343 to Darwin et al., Owned by the same assignee as the present application. The '343 patent comprises an imidized acrylic polymer or copolymer thereof that was unexpectedly found to provide a high degree of slump in cement mixtures over a long period of time without significant set delay. Discloses the use of the composition. This is disclosed, for example, in slump promoters based on alkenyl-ethers and acrylic acid or maleic anhydride proposed in Japanese Patent Publication Nos. 285140/88 and 163108/90, and in US Pat. No. 4,471,100. It was considered an improvement over copolymers made from the prepared hydroxy-terminated allyl ethers and salts, esters or amide derivatives of maleic anhydride.

[0005] Early attempts to formulate a water-reducing cement composition were disclosed in Japanese Patent Application Publication No. S.
52-76327 (published on June 27, 1977) by Inoue et al. This patent states that water weight loss agents such as, for example, lignin sulfonates and hydroxycarboxylates, result in poor concrete hardening when used in excess and sometimes cause accidents in which the resulting concrete structure falls off. To eliminate this effect, Inoue et introducing a composition made by reacting a gluconate compound or glucoheptonate such a C ₂ -C ₃ alkylene oxides using an alkali catalyst in the cement mixture Teach that poor curing can be overcome.

Japanese Patent Application Publication No. S58-15054 (published on Jan. 28, 1983) by Takemoto Yushi Co., Ltd., and Namotone sulfonic acid by Yamamoto et al. A concrete water reducing agent comprising a salt of formaldehyde condensate and a gluconate-ethylene oxide adduct was disclosed. This was said to provide high water resistance, prevent deterioration of the concrete due to slump changes over time, and avoid a set retarding effect that would impair initial strength.

Japanese Patent Application Publication No. S58-135 of Sanyo Chemical
165 and S58-135167 (release date: June 27, 1977)
(Tanaka) et al. Salts of naphthalenesulfonic acid-formalin condensates, cement setting retarders such as alkylene oxide adducts of carboxycarboxylic acids or polyhydroxy compounds (eg oxyalkylene adducts of gluconic acid), and glycol or glycerin and / or or C ₆ or less aliphatic mono - was disclosed or cement dispersing composition comprising an ester of a polycarboxylic acid.

[0008] US Patent No. 4,432,801 to Tegiacchi et al. Discloses a method for converting certain sugars, such as liquid glucose syrup, to the corresponding sugar acid salt or to the lower carboxylic acid salt. Was done. The resulting sugar material was then taught to be introduced into concrete to change its flowability.

SUMMARY OF THE INVENTION The present invention relates to altering the flowability, strength, milling efficiency, set retardation, and / or other properties of a cement, cementitious mixture, or other particle-containing composition. Preferred compositions of the present invention comprise a binder and one or more alkyl, aryl, alkylaryl, oxyalkylene, polyoxyalkylene groups, or mixtures thereof, with an amine, amide, imide, or urea group. And a compound having a sugar or sugar-derived group attached to a non-sugar substituent.

The term “additive” is sometimes used to refer to an agent introduced during the manufacture (eg, grinding) of cement, and the term “admixture” sometimes refers to a “cementitious composition”, such as concrete or mortar, Used to refer to agents that are combined in. However, for the purposes of the present invention, the term "cementitious composition" refers to a binder (cement, other cementitious binder), optionally volcanic ash, slag, clay, etc., and alters the properties of the cementitious composition For at least one compound (what is termed "additives" or "admixtures" is not strictly important).

[0011] Preferred compounds of the invention for use in modifying cementitious (other particle-containing) compositions are therefore (A) at least one group of a sugar or sugar derivative; at least one non - sugar substituents (preferably, C ₁ -C ₈ alkyl group which is not one substituted or substituted per one sugar groups in component (a)) such as an alkyl group, an aryl or alkylaryl group (preferably having a C ₆ -C ₈ aryl or alkylaryl group that is not one substituted or substituted per one sugar groups in component (a)), and / or oxyalkylene or polyoxyalkylene oligomer Or a polymer group (eg, a repeating C ₂ -C ₄ oxyalkylene group, or more preferably, a repeating ethylene oxide and propylene group). An amide, an amine for bonding the sugar group of component (A) to the non-sugar substituent of component (B), Comprising a linking group comprising an imide, urea, or a mixture thereof.

[0012] Exemplary sugar groups of component (A) include hydroxycarboxylic acids such as aldonic acids (eg, gluconic acid, heptogluconic acid), aldaric acids (eg, glycolic acid, heptoglycaric acid), and uronic acids (eg, glucuronic acid) , Heptoglucuronic acid), or their salts or their lactones (ie, anhydrides), or from aldoses or sugars (eg, monosaccharides, such as glucose, disaccharides, such as sucrose, etc.). Includes corn syrups and molasses, which can also be derived and also function as substrates for gluconamide production, and their oxidized forms.

Exemplary non-sugar substituents of component (B) are at least one substituted or unsubstituted alkyl, aryl, and / or alkylaryl group, and / or an oxyalkyl or poly or alkylene group. Comprising.
A substituted alkyl, aryl, or alkylaryl group is a functional group such as a hydroxy group, alkene group, alkyne group, halide group, ether group, carbonyl group, aldehyde group, ketone group, ester group, carboxylic acid group, amide group, Amine group,
A nitrite group, a nitro group, a sulfide group, a sulfoxide group, an amino acid group, a sulfonate group, a phosphonate group, or a mixture thereof may be included without departing from the present invention. If the saccharide group is derived from monomeric saccharide and the non-sugar substituent is an alkyl group, the alkyl group may be substituted with an alkyl group to provide adequate solubility and surface activity to all derived saccharide compounds. The number of carbon atoms should preferably be between 1 and 8.

Among the linking groups identified for component (C), one or more sugar groups are
Amides are most preferred for linking to one or more non-sugar substituents.

Preferred compounds of the present invention for modifying cement, cementitious compositions, or other particle-containing compositions include at least one group of sugars or sugar derivatives, C _2-
A C ₄ oxyalkylene group, or more preferably, a repeating unit having 2-20
At least one non-sugar substituent comprising 0 (and more preferably 2-100) repeating ethylene oxide and propylene oxide groups; and 1
One or more sugar groups to one or more non-sugar substituents, preferably an amide group. This compound is sold, for example, as a cement additive (eg, a grinding agent) or as an admixture for use in cementitious compositions (eg, concrete, mortar). The compounds are also believed to be useful as particle dispersants in non-hydratable particle-containing compositions (eg, clay-containing mixtures, latexes for coatings, and patches, sealants, or coating compositions).

The invention is particularly directed to cements and other cementitious or other hydratable binder compositions comprising the above-described additives or admixture compounds (as well as non-hydratable non-hydratable binder compositions). Composition). The present invention also relates to methods for modifying such compositions, as well as methods for making the compounds described above.

In addition to the ability to alter the flow properties of cement and cementitious compositions, the compounds described above can also be used to alter other properties of the cementitious composition. For example, the compounds are useful as grinding aids for cement clinker, and therefore, the methods of the present invention involve the introduction of the compound during the grinding of cement clinker. When used as a grinding aid, the compounds of the present invention are believed to be useful for increasing the strength of materials and structures made from the treated cement.

The compounds described above may be used as effective water-loss additives in or for use with cement, in the manufacture of cement, and cementitious mixtures including concrete, mortar, or mesonries. Suitable for use in. In addition to the ability to alter the flow properties of cement and cementitious compositions, these compounds can be used to alter other properties of the cementitious composition. For example, these compounds are believed to be useful as grinding aids for cement clinkers, and as a result, a preferred method of the present invention is to incorporate the above-described additive compounds during grinding of the cement clinker. Is included. When used as grinding aids, these compounds are believed to be useful for increasing the strength of materials and structures made from the treated cement.

It is further believed that the compounds described above, when used as admixtures, provide advantages as water loss agents for cement and cementitious compositions. Therefore, an exemplary method of the present invention involves the introduction of the compound into an aqueous environment having a binder material. For example, the composition can be introduced as an admixture in concrete or mortar, together with a hydratable and / or non-hydratable binder material (eg, cement and / or clay), or mixed with water. Can be introduced.

On a general basis, the compounds according to the invention can be used as dispersants for a plurality of particles to be dispersed, for example calcium carbonate, which is technically not a hydratable binder per se. . Thus, the compositions of the present invention include a plurality of particles to be dispersed and a plurality of particles-dispersing compound, wherein the compound comprises at least one group of a sugar or sugar derivative, at least one non-sugar-substituted compound. Group, and a linking group.

The present invention also provides non-hydratable solids, such as polymer particles (eg, synthetic polymers for latex) or minerals (eg, calcium carbonate), as described above, with non-sugar substituents attached by a linking group. It also relates to a method of dispersing a non-hydratable solid in an aqueous system comprising introducing a compound described herein having an attached sugar group. Therefore,
An exemplary composition comprises a plurality of particles to be dispersed and a compound for dispersing the plurality of particles, wherein the compound comprises at least one of (A) a sugar or a sugar derivative.
Two groups, (B) at least one non-sugar substituent, for example an alkyl group (preferably one substituted or unsubstituted C ₁ -C ₈ alkyl group per sugar group in component (A)) ), Aryl or alkylaryl groups (preferably one substituted or unsubstituted C _6- per sugar group in component (A))
C ₈ having an aryl or alkylaryl group), and / or oxyalkylene or polyoxyalkylene oligomer or polymer group (e.g., have a repeat C ₂ -C ₄ oxyalkylene groups or more preferably repeating ethylene oxide and propylene oxide groups, Wherein the number of repeating units is 2-200), and (C) an amide, an amine, an imide, an urea for bonding the sugar group of the component (A) to the non-sugar substituent of the component (B), Or a linking group comprising a mixture thereof.

[0022] An exemplary method for making a sugar amide compound is also disclosed herein. An exemplary method comprises introducing a sugar derivative and an amine (and optionally a solvent) into a mixing vessel to form a reaction mixture, and producing a sugar amide reaction product. The sugar amide reaction product can then be separated from the reaction mixture solvent. The components can be added using conventional methods. For example, the sugar derivative component can be introduced into the mixing tank using a bulk solid hopper and a feed system.

Another exemplary method involves evaporating the reaction mixture solvent and isolating the sugar amide reaction product as a dry substance. In another exemplary method, the pressure on the reaction mixture is increased by (
Evaporation can be performed by reduction (eg, by application of a vacuum), thereby removing the solvent from the sugar amide reaction product. The solvent can also be removed by flowing a gas over or through the reaction mixture. Yet another good example is
The sugar amide reaction product forms a precipitate. Before removing the resulting crystals by filtration,
The reaction product can be optionally cooled. Next, a dried product can be obtained by evaporating the remaining solvent.

Another preferred method of the present invention involves the use of water to extract the sugar amide reaction product from a solvent. Therefore, the water-immiscible solvent and the reaction product are contacted with water, for example, by countercurrent extraction, and the product is removed from the solvent phase to yield an aqueous phase product.
This exemplary scheme offers advantages in avoiding handling of solids and eliminating the need to evaporate or distill the solvent.

Yet another exemplary method of the present invention involves the use of water to replace the solvent after the reaction is completed. After the reaction is completed in the batch vessel, the solvent can be replaced with water using batch distillation. During displacement and / or solvent recovery, water is added continuously or all at once to the mixture containing solvent and product. Like the extraction method described above, this solvent displacement method offers the advantage of eliminating the need for handling solids and condensing the solvent from the carrier stream. In another exemplary method, the components are added into a continuous in-line mixing vessel to obtain the sugar amide reaction product, which is fed with the solvent (and residual amine, if present), and then continuously to a distillation column. be able to. The solvent is displaced by water that has been heated and evaporated in a distillation column, and the reaction product can be removed from the column in aqueous form, the solvent is condensed, optionally refluxed, and (along with any remaining amine, if present). ) Purified for reuse.

[0026] Other advantages and features of the present invention are disclosed below.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to particles which are to be dispersed (for example, fillers such as calcium carbonate,
Compositions and methods that include a binder, such as cement, slurry-like particles, such as drilling mud, and a compound for dispersing or otherwise modifying the particles. In particular, the invention relates to a cementitious composition comprising a cement binder and a modifying compound.

The terms “cement” and “cementitious composition” (these are “cement compositions”)
May be synonymous with) dry powder and paste, mortar,
It can be used to refer to a grout, such as an oilfield cemented grout, and a concrete composition comprising a hydratable cement binder. The terms “paste”, “mortar” and “concrete” are industry terms, and paste is a hydratable cement binder (typically, but not limited to, Portland cement, mesonry cement, or mortar cement) And limestone,
A mixture of hydrated lime, fly ash, blast furnace slag, volcanic ash, silica fumes, or other substances commonly found in such cements) and water; Concrete and mortar are pastes that also include coarse aggregate (eg, crushed gravel, stone). The cementitious compositions tested in the present invention produce the required amount of certain materials, such as hydratable cement, water, and fine and / or coarse aggregate to produce a particular cement composition. It can be manufactured by mixing, as applicable.

Exemplary Compounds for Modifying One or More Properties of Cementitious Composition
Are, as summarized above, groups of sugars or sugar derivatives, non-sugar substituents, and
Comprising a binding member for attaching a sugar group to a non-sugar substituent. Such compounds
Is the following equation [G]_g[X]_x[Q]_q Wherein G represents at least one group of a sugar or a sugar derivative, and “g” is 1 to 10
Is an integer of 0, and more preferably "g" is 1-50, and X is an amide,
Represents a linking group selected from amines, imides, ureas, or mixtures thereof (
Preferably it is an amide), "x" is an integer from 1 to 100 (and preferably
Q is preferably less than or equal to "q", and Q is alkyl (preferably
One substituted or unsubstituted C per sugar group in component (G) _Two -C₈Having an alkyl group), an aryl or alkylaryl group (preferably
Represents one substituted or unsubstituted C per sugar group in component (G) ₆ -C₈Having an aryl or alkylaryl group), and / or oxy
Alkylene or polyoxyalkylene oligomer or polymer group (eg,
, Preferably repeating C_Two-C_FourAn oxyalkylene group, or more preferably,
Having repeating ethylene oxide and propylene oxide groups, where
The number of units is 2-200), and "q" is an integer of 1 to 100].

When “g” is 1, “[G]” will represent a monomeric sugar group.
If "g" is greater than 1, there will be more than one "[G]" group. In other words, there can be more than one [G] group attached to the linking group "X" or indirectly attached to another [G] group. Therefore, the formula [G] _g [X] _x [Q] _q is, for example, the formula

[0031]

Embedded image

Wherein multiple sugar groups (G) are linked to one another and one sugar group is linked to linking group (X), and can include the structure represented by the formula [G ] _g [X] _x [Q] _q is, for example, a structure shown below

[0033]

Embedded image

It can be understood that these variations are also included. It is understood that "G", "X", and "Q" can represent the same or similar groups, units, or compounds.

Similarly, for non-sugar substituents represented by [Q] _q , the formula can be of various structures, for example:

[0036]

Embedded image

It will be appreciated that these and variations thereof can be encompassed.

In consideration of this disclosure, the sugar group and the non-sugar substituent component have a linking member (X) and the following structure:

[0039]

Embedded image

It will be appreciated that the same can be attached to other similar or identical groups or compounds as in other variations. Part of the above “G” and / or “Q” groups is G, Q
, GX, XQ, and / or other variants that can be attached to groups containing GXQ can be made.

As used herein, the term “sugar group” refers to a sugar molecule (eg, a monosaccharide, disaccharide, polysaccharide, etc., as further described below) or a sugar molecule that can be chemically attached to a linking group. Derivatives are meant and referred to.

A particularly preferred compound of the present invention comprises a sugar amide ("[G] _g [X] _x " component) for altering the flowability of cement, mortar, or concrete. This preferred embodiment can be derived from hydroxycarboxylic acids, such as sugar acids, and amines. For example, the sugar group "G" may be a hydroxycarboxylic acid such as aldonic acid (eg, gluconic acid, heptogluonic acid), aldaric acid (eg, glycaric acid, heptoglicaric acid), and uronic acid (eg, glucuronic acid, heptoglucuronic acid) Alternatively, it can be derived from glucoheptonic acid, sometimes named otherwise), or their salts or their lactones (ie, anhydrides).
Sugar groups can be derived from aldoses or sugars (eg, glucose, sucrose, tetroses, pentoses, hexoses, etc.), and corn syrups and molasses and their oxidized forms, which can also serve as substrates for glucoamide production. Include.

Preferred saccharide groups are those having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and most preferably 5 to 7 carbon atoms. These also preferred saccharide acids include D-gluconic acid, D-glucaric acid, and D-glucuronic acid, and mixtures thereof.

As mentioned above, the non-sugar substituent “Q” groups include, for example, hydroxy, alkene, alkyne, halide, ether, carbonyl, aldehyde, ketone,
Ester group, carboxylic acid group, amide group, amine group, nitrite group, nitro group,
It can comprise substituted alkyl and aryl groups having a functional group such as a sulfide group, a sulfoxide group, an amino acid group, a sulfonate group, a phosphonate group, or a mixture thereof.

The alkoxylated amine which can be used to obtain the additive / admixture compounds of the invention in combination with the starting sugar acid is therefore of the formula

[0046]

Embedded image

Wherein AO represents an alkoxy group, and preferably a C ₂ -C ₃ ethylene oxide / propylene oxide group, and “n” and “p” are those wherein the sum of “n” and “p” is 1-100. Is an integer such that "n" or "p" is individually 0-1
And R ¹ and R ² each represent hydrogen or a substituted or unsubstituted C ₁ -C ₈ alkyl, aryl, or alkylaryl group, and when “n” = 0 Wherein the corresponding R ¹ comprises an alkyl, aryl, or alkylaryl group (preferably having up to 8 carbon atoms). Also, R ¹ can combine with R ² to form a cyclic polyoxyalkylene secondary amine, such as morpholine.

Thus, the alkylamines that can be used to obtain the additive / admixture compounds of the present invention in combination with the starting sugar acid have the formula

[0049]

Embedded image

Wherein R ³ and R ⁴ independently represent hydrogen or a C ₁ -C ₂₀ alkyl group, a cycloalkyl group, or an aryl ring (such as in benzylamine). . R ³ and R ⁴ can also form a cyclic structure as in, for example, a cyclic secondary amine, such as piperazine. R ³ and R ⁴ can also contain additional amines or other functional groups.

The amine can be reacted with the sugar acid by thermal amidation, with or without an amidation catalyst. The reaction temperature is preferably in the range from 80 to 180 ° C (more preferably 100-145 ° C) and the reaction can be performed in bulk or in solution. An azeotropic agent, such as toluene, can be used to promote dehydration. Lactone formation can be minimized by using a slight to moderate excess of the amine, and it is believed that the residual amine has no adverse effect on the cementitious material that introduces compounds containing sugar groups. .

The derived sugar amide has the general formula:

[0053]

Embedded image

Wherein G ¹ represents a monomeric sugar group after amidation, wherein the C ＝ O moiety involved in the amide bond is first derived from G and where the sugar acid is non- Reacting with a sugar amine and G ¹ can be in either a linear or cyclic form depending on the amine species and / or ambient environment, AO is a C ₂ -C ₄ alkoxyl group, and more preferably ethylene oxide and propylene Represents an oxide group, R ¹ and R ² independently represent hydrogen or a C ₁ -C ₃ alkyl group, “n” and “p” each independently represent an integer from 0 to 100; and the sum of "p" is an integer from 1 to 100, and R ³ and R ⁴ are independently hydrogen or C ₁ -C ₂₀ alkyl, cycloalkyl or aryl ring (e.g., such as in benzylamine )] It can be more representative. R ¹ , R ² , R ³ and R ⁴ can also contain functional groups.

An amine can also be reacted with a saccharide or oligosaccharide having a reactive aldehyde or ketone group to form an adduct. The reaction temperature is 0 to 120 ° C, preferably 2
0 ° C to 100 ° C. The reaction can be carried out in a substantially bulky, small amount of water (fusing the sugar with the amine), alcohols, alcohols containing water or water. The sugar amine adduct is converted to an Amadori derivative (in the case of reaction of an aldose with an amine) using an acid catalyst such as hydrochloric acid, acetic acid, oxalic acid, etc.
It can be rearranged into a more stable form known as (Heyns) compounds (in the case of the reaction of ketoses with amines).

After rearrangement using an acid catalyst, an exemplary sugar-amine adduct has the general formula:

[0057]

Embedded image

[Wherein, G ² represents a monomeric sugar group after an amination reaction between the sugar and the non-sugar amine;
Here AO is an alkoxy group, and preferably represents a C ₂ -C ₃ ethylene oxide and propylene oxide groups, "n" and "p" are integers the sum is such that 1 to 100 of "n" and "p" And “n” and “p” are 1-100
And R ¹ and R ² each represent hydrogen or a (substituted or unsubstituted) C ₁ -C ₈ alkyl, aryl, or alkylaryl group, and when “n” = 0, Wherein the corresponding R ¹ comprises an alkyl, aryl, or alkylaryl group (preferably having up to 8 carbon atoms). Also, R ¹ can combine with R ² to form a cyclic polyoxyalkylene secondary amine, such as morpholine. R ³ and R ⁴ independently represent hydrogen or C ₁ -C ₂₀ alkyl, cycloalkyl group, or aryl group (for example, benzylamine). R ¹ , R ² , R ³ , or R ⁴ can also contain other functional groups.

Hydrogenation of sugar amine adducts can also be performed to stabilize the compounds and improve their dispersing performance. Hydrogenation can be carried out simultaneously with the formation of the amine adduct, with or without a catalyst. The derived hydrogenated sugar-amine adduct has the general formula:

[0060]

Embedded image

Wherein G ³ represents a monomeric sugar group after amination and subsequent hydration, wherein AO represents an alkoxy group, and preferably a C ₂ -C ₃ ethylene oxide and propylene oxide group. And “n” and “p” are such that the sum of “n” and “p” is 1 to
Are integers such that 100, and "n" and "p" is 1 to 100, and R ¹ and R ² (not or substituted substituted) each hydrogen or C ₁ -C ₈ alkyl , Aryl, or alkylaryl groups; and
When n "= 0, the corresponding R ¹ comprises an alkyl, aryl, or alkylaryl group (preferably having up to 8 carbon atoms). Also, R ¹ can combine with R ² to form a cyclic polyoxyalkylene secondary amine, such as morpholine. R ³ and R ⁴ independently represent hydrogen or C ₁ -C ₂₀ alkyl, cycloalkyl group, or aryl group (for example, benzylamine). R ¹ , R ² , R ³ , or R ⁴ can also contain other functional groups.

The cements and cement compositions of the present invention may be used in an amount of 0.001 to 0.001 based on the weight of hydratable cement, or other cementitious binder, and hydratable cement.
Comprising 5.0% by weight of a mixture of the above sugar-amine derivative compounds. More preferably, the amount of the sugar-amine derivative compound in the cement or cement composition is from 0.0005 to 0.5, based on the weight of the hydratable cement or cementitious binder.
% By weight.

Although not confirmed by theoretical considerations, the inventor has now shown that, for cementitious compositions, the preferred [G] _g [X] _x [Q] _q compound is a particle binding group (eg, Non-sugar substituent component Q to provide steric hindrance and / or rebound to provide an advantageous rate of adsorption for cement particles to enhance and disperse and combine and disperse within the aqueous matrix of the cementitious slurry Present their belief in providing a sugar moiety G) linked by an intervening linking group X to
Before being bound by the cement or all adsorbed onto the cement, such compounds as set forth herein begin to disperse uniformly in the cementitious composition, such as mortar or concrete.

The present invention also provides compounds of the present invention, which are useful for modifying hydratable compositions (eg, mortar, concrete) and non-hydratable particle-containing compositions as well.
Novel methods for producing, for example, sugar amide derivatives are also provided.

As shown in FIG. 3, an exemplary method for making a sugar amide derivative is to combine an amine component 10, a sugar derivative 12, and optionally a solvent 14 in a mixing vessel 20 to form an amine component. The reaction of linking 10 and the sugar derivative via an amine bond is initiated.

After the product has formed, it must be separated or removed from the solvent, in order to provide sufficient contact between the two reactants to promote the formation of the sugar amide derivative product. Working, it is indicated as 22 in the solvent removed from the mixing vessel 20.

The amine component 10 can comprise a wide range of primary alkyl amines, secondary alkyl amines, or aromatic amines. Amine to sugar derivative component 12
In a molar ratio of about 1: 1. A small excess of the amine (eg, 3 mol%) can be added to complete the reaction. Amines of particular interest include primary and secondary amines as well as primary or secondary amines containing a functional group.

The sugar derivative component 12 may comprise a sugar or a salt thereof or an acid derivative of a lactone (eg, glucono-delta lactone). The solvent provides the appropriate contact between the two reactants to initiate the reaction.

The solvent 14 can preferably be chosen such that it is miscible with the amine component 10. Dissolution of the sugar derivative 12 is believed to be essential for product formation, but is advantageous in increasing the reaction rate. Further, in some isolation schemes,
The nature of the solvent may be such that the reaction product is soluble in the solvent under the reaction conditions, but upon cooling (to room temperature or below) the product may precipitate or crystallize from the reaction solvent. It is advantageous. Sufficient amount of solvent 14 should be used to completely dissolve amine component 10 and dissolve or wet sugar derivative 12. Solvents contemplated for use include alcohols and other polar organic solvents (eg, chlorinated hydrocarbons, ethers, amides, nitriles), aromatic hydrocarbons,
Tertiary amines (eg, triethylamine, triethanolamine, methyldiethanolamine, trispropanolamine, etc.), and amines used as reactants (introduced into the amine component 10) are included. Methanol is the most preferred solvent in terms of accelerating the reaction. However, other solvents are also suitable and can facilitate the isolation step as discussed further below.

The mixing step (denoted at 20) can be performed at room temperature, or more preferably, at a slightly higher temperature and / or atmospheric pressure. Since the reaction is exothermic, it is believed that the reaction itself results in an increase in temperature within the mixing vessel 20. This can advantageously increase the reaction / production rate. In some cases, gentle heating can be applied to increase the speed (eg, in the mixing vessel 20). The reaction may be carried out using refluxing methanol, but this is not essential for the reaction to take place.

The isolation of the product, such as the drying step, indicated at 28 in FIG. 3, may be the step that has the greatest impact on the process scheme. As shown in FIG. 3, isolation of product 30 drives off residual solvent, for example, by using any known direct or indirect heating method, and then vacuum and / or purge gas (labeled at 29) To remove the solvent and obtain a separated dry reaction product 30. Preferably, the solvent is then condensed 32 and mixed tank 2
Before being returned to the solvent recovery tank 14, which is also used as raw material into the wastewater, it is purified 34 if possible, for example by distillation, filtration through activated carbon or other known methods. Off-gas 35 from condenser 32 is preferably recovered (eg, flushed) and reused in this manner. The choice of solvent in this case is dictated by the ability of the process to easily evaporate the remaining material. Such solvents can include low molecular weight alkyl alcohols, and especially methanol, as described above.

Another exemplary method for product isolation is shown in FIG. 4, where the reaction is carried out in a mixing vessel 20.
After starting in, the sugar amide derivative reaction product in the solvent is then preferably
6, and optionally and preferably in a separation crystallization tank 26 (
Alternatively, crystallize by using common cooling means (through a cooling coil (indicated by 24)). The crystallized or precipitated reaction product can then be filtered 27 from the solvent mass, which can be returned to the solvent bath 14, preferably after purification 34. Filtration can be performed in a wide range of modes, for example, batch cake filtration (eg, pressure leaf or Nutsche filter), continuous cake filtration (eg, disk or horizontal vacuum filter), or centrifugal filtration (eg, basket, peeler, or pusher). it can. The resulting cake may undergo further drying using the standard procedures described above. The filtered solvent 27 can then be purified 34, for example by filtration using activated carbon, and reused in this way (by feeding back to the solvent bath 14). The residual solvent remaining with the filtered reaction product undergoes a drying step 28, where the residual solvent is removed by direct or indirect heating 28.
The reaction product 30 which is driven out and separated can be obtained. Purge gas,
A vacuum, or both 29, can be used to facilitate removal of the residual solvent, which is then condensed 32, optionally purified (as described above) 34, and for reuse in this method It is returned to the solvent tank 14. Off-gas 35 can be recovered (eg, purged with a condenser) and reused in this manner.

[0073] The crystallization mode offers advantages that include a significant reduction in the amount of solvent condensed from the carrier stream. For example, the number of solvent recovery stages shown in FIG. 4 illustrates this advantage. The choice of solvent is important because the product must be soluble at the reaction temperature but the reaction product is preferably almost insoluble at the crystallization temperature. Isopropanol and methanol are particularly useful solvents at ambient temperature (eg, about 70 ° F.)
Gives almost complete recovery of the product.

Therefore, an exemplary method for producing a sugar amide derivative of the present invention is to introduce a sugar derivative, an amine, and a solvent into a mixing vessel to form a reaction mixture, and to produce a sugar amide reaction product. And separating the sugar amide reaction product from the reaction mixture solvent. The sugar derivative can comprise, for example, a sugar or a sugar acid derivative of the salt or lactone thereof. The amine component is aromatic, hydroxy,
Primary amines, secondary amines, or mixtures thereof, comprising groups selected from ether, halogen, unsaturated alkyl, carbonyl, ester, amino, nitro, carboxylic acid, nitrilo, thio, or sulfone functional groups Can be included. In an exemplary method, the solvent is an alcohol, a polar organic solvent (eg, a chlorinated hydrocarbon, ether, amide, nitrile, or mixture thereof), an aromatic hydrocarbon, an amine (eg, preferably a tertiary amine). Or mixtures thereof. Mixing vessel 20 may further comprise a batch mixing vessel, where the reaction is substantially complete (and / or periodically).
Valves and / or tubes are opened, thereby carrying the reaction-product / solvent (22) to the drying stage 28, and the mixing vessel 20 can be a continuous in-line vessel, from which crystallization or precipitation can occur. The reaction product obtained is passed in a continuous manner to the drying stage 28 in a solvent.

The drying of the sugar amide reaction product shown at 28 can be carried out by heating as described above (
For example, it can be performed (by exposure to an applied direct heat source, such as by thermal energy, or a heated tube), but it is recommended that the sugar amide derivative not be carbonized by overheating or unnecessarily high thermal energy. In another exemplary method, the solvent is removed from the sugar amide reaction product by flowing gas through the reaction product and / or by applying a vacuum.

In another exemplary method of the present invention, the cooling step 24 is preferably mixed with the amine 10, the sugar derivative 12, and the solvent 14, and then used to crystallize or precipitate the reaction product. This facilitates subsequent filtration of the reaction mixture solvent, causing the sugar amide reaction product to separate from the solvent.

Another preferred method of the present invention for producing a sugar amide derivative involves the use of water to extract the product from the solvent. As shown diagrammatically in FIG. 5, the amine component 10, the sugar derivative component 12, and the solvent 14 are mixed together 20 and the resulting reaction product in the solvent is fed to an extraction column or vessel 40. . Extraction column 4
0, the solvent containing the reaction product contacts the water flowing through the column 40 in such a way that the reaction product flows in a direction that is countercurrent to the direction of the water flow. The reaction product is removed from the bottom of the extraction column 40 as an aqueous product 44, and the solvent is then collected at the top of the extraction column 40 and, after an optional purification step 34, for reuse in this method Is returned to the solvent recovery tank 14.

The solvent 14 used in the reaction step 20 must be immiscible with water in order to make the extraction feasible. A suitable solvent for this purpose is toluene. Other exemplary solvents that are believed to be suitable are anisole, benzene, acetonitrile, xylene,
And methyl butyl ether (preferably methyl-t-butyl ether).

One important consideration in the exemplary reaction scheme shown in FIG. 5 is that residual amine may degrade the reaction product in the presence of water. This can be overcome by adding a buffer with the water 42 introduced into the extraction column 40 to adjust the pH. Examples of buffers and pH adjusters include the common ones (commercially available buffer solutions), ionic polymers, acetic acid, hydrochloric acid, nitric acid, mineral acids and carboxylic acids, ammonium chloride, or mixtures thereof.

Yet another method for producing sugar amide derivatives involves solvent displacement distillation.
Like the extraction method, the solvent displacement distillation method as shown in FIG. 6 offers the advantage of eliminating solid handling and the need to condense the solvent from the carrier stream. As shown in FIG. 6, in this case, the solvent 14 and the amine component 20 are combined with the sugar derivative component 12 in a mixing tank 20 which is a batch container. After the reaction is completed, the solvent is replaced by water 42, which is introduced continuously or directly in doses into a mixing vessel 20 containing the solvent and the reaction product, preferably together with a pH buffer. I do.
By heating the solvent, for example by using a distillation column 50 connected to the mixing vessel 20, it is driven off and separated from the water using batch distillation. The reaction product is then recovered as aqueous product 30. Solvent traveling through distillation column 50 can be condensed using condenser device 32 and refluxed in column 5. Finally, the recovered solvent can optionally (and preferably) be subjected to purification using activated carbon or other filtration methods before being reused in a subsequent batch. Solvent selection is important because the separation from water must be almost complete for reuse in subsequent reactions. Solvents such as methanol are preferred because they do not form azeotropes with water. Other alcohols can be used, but the reaction rate is slowed because a small amount of water tends to be recycled with the solvent.

An important consideration in the solvent displacement regime, as in the extraction process, is that the residual amine will degrade the product in the presence of water and at elevated temperatures. This can be overcome by adding a buffer with water and adjusting the pH, as described above. Alternatively, vacuum suction on the mixing vessel (to reduce pressure) helps reduce degradation by lowering operating temperatures.

Another exemplary solvent displacement method is illustrated graphically in FIG. In this case, a continuous reactor (eg, in-line, continuous stirring and mixing tank 22) is used to continuously react the amine component 10, the sugar derivative component 12, and the solvent 14 together. The reaction product in solvent (20) is continuously fed to distillation column 50, where water 42 displaces the solvent. Water 42 is introduced at or near the bottom of distillation column 50 (optionally with one or more pH buffers), where a heating element or "reboiler" 52 is used to heat the distillation column. Water functions to displace the solvent and the reaction products are removed in aqueous form. The solvent is then condensed using a condenser 32 and optionally purified, for example using activated carbon filtration 34, and then the solvent is recovered (along with unreacted amine) 14 and can be reused in this manner. This approach (FIG. 7) has an additional advantage over the batch method (shown in FIG. 6) because the residual amine is removed before it is combined with a significant amount of water. This can reduce degradation and eliminate the need for buffer or vacuum operations.

The above-mentioned compounds of the invention may be converted into conventional admixtures, such as alkoxylated polycarboxylates (eg “comb” type polymers used as water-reducing agents or superplasticizers, such as Grace Construction® Products (Grace Construct
ion Products), Cambridge, super plasticizers commercially available under the trade name "ADVA ^R 'from MA), naphthalene sulfonate formaldehyde condensates, melamine sulfonate formaldehyde condensate, calcium or sodium lignosulfonate, alkali or alkaline earth metal Nitrite or nitrate (eg, calcium nitrite and / or calcium nitrate, such as Grace
Those available from Construction Products under the trade name "DCI ^R", sodium nitrite and / or sodium nitrate, nitrite and / or potassium nitrate, etc.), or contraction - reduced admixture, for example alkyl ether oxyalkylene adduct And / or those containing oxyalkylene glycols (for example, trade name “ECLI” from Grace Construction Products)
It can be combined with one) commercially available as PSE ^R ".

The following examples can further facilitate an understanding of the advantages or features of the present invention.

Example 1 Preparation of N-Methoxypropyl Gluconamide 20 grams in a 4-neck flask equipped with a mechanical stirrer, DEAN-STARK ^™ trap with condenser, dry nitrogen inlet, and thermocouple Gluconic acid (50% by weight, obtained from Aldrich Chemical) (51 mM) and 4.54 grams (51 mM) of methoxypropylamine (available as "MOPA" from Huntsman Chemical) Are mixed at room temperature. The homogeneous mixture is then cooled to 145 under a slow continuous stream of nitrogen.
Heated to ° C. The solvent water was removed during the heating step. After the temperature reached 145 ° C., the reaction mixture was kept stirring for 2 hours. A dark brown to black sticky syrup was obtained. The product was dissolved to give a 10% aqueous solution. PH of the resulting solution
Was 4-6.

Example 2 Preparation of N-methoxyoxypropylene- 2 -propylgluconamide The used amine was 7.49 grams (51 mM) of methoxyoxypropylene-
The procedure of Example 1 was followed except that it was 2-propanamine (available from Huntsman Chemical). The resulting solution pH was 4-6.

[0087] Example 3 N-polyoxyethylene alkyl (MW = 715) commercially available from Huntsman Chemical amine prepared using the gluconic amide 35.7 g (51 mM) Jeffamine (JEFFAMINE) ^R M715 (MW = approximately 715, EP / PO molar ratio =
13/2), except that it was a monomethoxypolyalkylene oxide monoamine available as 13/2). The resulting solution pH was 5-6.

[0088] Example 4 N-polyoxyethylene alkyl (MW = 2000) commercially available from Huntsman amine prepared using the gluconic amide 102 g (51 mM) Jeffamine ^R M 2070 (MW = about 2000, EP / PO molar ratio = 32 / 10), except that it was a monomethoxypolyalkylene oxide monoamine available as / 10). The resulting solution pH was 4-6.

Example 5 Preparation of N-Polyoxyalkyl (MW = 3000) Gluconamide The amine used was POLYETHERAMINE M3000 from BASF with 153 grams (51 mM) (MW = about 3000, EP / PO). Molar ratio =
Example 1 was followed except that it was a monomethoxypolyalkylene oxide monoamine available as 0.85). The resulting solution pH was 4-6.

Example 6 Preparation of N-2-hydroxyethylgluconamide (gluconic acid / ethanolamine) In a round bottom flask equipped with a mechanical stirrer and a Dean-Stark ^™ trap with a condenser, 6.1 g of ethanolamine ( 100 mM) sample was dissolved in about 250 mL of toluene. Gluconic acid (50% by weight) (100m
A 39.2 g sample of the aqueous solution of M) was added. The mixture was then heated to reflux until the evolution of water ceased. Toluene was removed by decanting. The residual sticky brown solid was dissolved in water. The product was dissolved to give a 48% aqueous solution. The pH of the resulting solution was 4.7.

Example 7 N-methoxypropylheptogluconamide (sodium glucoheptonate / M
Production of OPA) Dissolve an 8.9 g (100 mM) sample of methoxypropylamine (MOPA, Huntsman Chemical) in approximately 250 mL of toluene in a round bottom flask equipped with a mechanical stirrer and a Dean-Stark ^™ trap with a condenser. I let it. An 8.3 mL (100 mM) sample of hydrochloric acid (12.1 M) was added with stirring. 7 of an aqueous solution of sodium glucoheptonate (50% by weight) (100 mM)
A 5.2 g sample was added. The mixture was then heated to reflux until the evolution of water ceased.
Toluene was removed by decanting. The residual sticky brown solid was dissolved in water. The product was dissolved to give a 45% aqueous solution. The pH of the resulting solution was 4.7.

Example 8 Preparation of N-hexylgluconamide (delta-gluconolactone / hexylamine) In a round bottom flask equipped with a magnetic stirrer and reflux condenser,
Six grams of gluconolactone (33.7 mM, Aldrich Chemical Company) were dissolved in 115 mL of refluxing methanol. A 3.5 gram sample of hexylamine (33.7 mM, Aldrich Chemical Company) was added and the mixture was allowed to reflux with stirring for 90 minutes. The reaction mixture was cooled to room temperature and the solvent was removed by rotary evaporation. The product, a white crystalline solid, was recrystallized in a solution of methanol: tetrahydrofuran. The product was dissolved in water to give a 1% aqueous solution. Solution pH
Was 7-9.

Example 9 Preparation of N-butylgluconamide (□ ta-gluconolactone / butylamine) 10.0 g (56.0 g) of □ -gluconolactone in a round bottom flask equipped with a magnetic stirrer and reflux condenser. 2 mM, Aldrich Chemical Company) was dissolved in 200 mL of refluxing methanol. Butylamine (56.2
A 4.10 gram sample of Ca.mM (Aldrich Chemical Company) was added and the mixture was allowed to reflux with stirring for 90 minutes. The reaction mixture was cooled to room temperature and the solvent was removed by rotary evaporation. The product was a white crystalline solid. The product was dissolved in water to give a 10% aqueous solution. PH of the solution is 4
-6.

Example 10 Mortar Test Procedure 760 g of Ordinary Portland Cem
ent) (Type 1) with 1575 g of sand (SSD specification of Mesonry sand, SG = 2.6)
A mortar mixture containing 5) and 334 g of water was prepared. The admixture dose is reported as a percentage (by weight of cement). Mortar to hobart (H
(OBART) ^™ mixer for 5 minutes, then measured slump, slump-flow distance, and air content. Slump was measured by placing the mortar mixture into a slump cone and flowing the conical sample over a table, removing the cone, and then measuring the drop in height of the conical sample. .
The used cone dimensions are Japanese Industrial Standard (JIS) A1173 (cone height = 15
0 mm, upper diameter = 50 mm, lower diameter = 100 mm). At the same time, the slump-flow distance (extended diameter) was measured. Air content was measured according to ASTM C185. After the test, the mortar mixture was used for measuring the setting time. Since the cure time was measured using an automatic penetrometer developed by WR Grace & Co.-Connecticut, the measured cure time was ASTM C403 / C403M-95. Equal to the initial cure time defined by

The results are shown in Tables 1-4 below and FIGS. 1 and 2. In FIG. 1, the flow performance (flow distance (mm)) of Examples 1 and 5 is compared with that of gluconic acid as a function of the dose. FIG. 2 shows the cure delay performance with respect to cure time (hours) as a function of dose for Examples 1, 5 and unmodified gluconic acid.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

Example 11 Concrete Testing Steps Concrete testing was performed using the following mixture design and units are given in pounds per cubic yard (lbs / cyd) (Table 5). 30 liters of concrete were mixed with a drum mixer for 9 minutes. The admixture was added to the concrete while mixing with the water. The admixture dose is reported as a percentage (by weight of cement).

[0101]

[Table 5]

The test results are shown in Table 6 below. For some doses, gluconamide or glucoheptoamide showed less delay and equivalent or improved slump than gluconic acid.

[0103]

[Table 6]

Example 12 Preparation of N-polyoxyalkyl (MW = 700) -glucamine 10 grams of glucose in a 4-neck flask equipped with a mechanical stirrer, Dean-Stark ^™ trap with condenser, and dry nitrogen inlet The sample was dissolved in 10 grams of water at 60-80 ° C. A homogeneous syrup was obtained within 20 minutes. To the syrup was added 0.19 mL of 5N aqueous HCl, then 3
8 grams (mM) of Huntsman Chemical from Jeffamine ^R M715 (trade name)
A monomethoxypolyalkylene oxide monoamine, available as MW = about 715, EP / PO molar ratio = 13/2) was added. The homogeneous mixture was then heated to 110 ° C. in a oil bath for 3 hours under a slow continuous stream of nitrogen. The color of the homogeneous mixture rapidly changed from yellow to green and then a deep yellow color was obtained. The mortar test results for the materials are found in Table 7 along with those for D-glucose. The mortar test process is Example 1
The same as described in No. 0.

[0105]

[Table 7]

Example 13 Preparation of a Glucose-Ethanolamine Adduct A 20 gram sample of glucose (11 mM) in a 4-neck flask equipped with a mechanical stirrer, Dean-Stark ^™ trap with condenser, and dry nitrogen inlet, 6 .78 grams of ethanolamine (111 mM), 6.67 grams of acetic acid (111 mM), and 2.5 grams of water were melted at 60-80 ° C. The homogeneous mixture is then placed in an oil bath for 30 minutes under a slow continuous flow of nitrogen for 11 minutes.
Heated to 0 ° C. The pressure in the flask was then increased to 35-50 mmHg for 40 minutes.
And the water was removed. A very sticky black syrup was obtained. The mortar test results for the materials are shown in Table 8 along with those for D-glucose. The mortar test procedure was the same as described in Example 10.

Example 14 Preparation of Hydrogenated Glucose-Ethanolamine Adduct 20 grams of glucose (111 mM) in a four-neck flask equipped with a mechanical stirrer, Dean-Stark ^™ trap with condenser, and dry nitrogen inlet.
A 0.0 gram sample was dissolved in 20 grams of water at 60 ° C. 5N HC
Add a 0.19 mL aliquot of the aqueous solution. After 15 minutes, 6.97 grams (11
4 mM) monoethanolamine was added to the flask. The temperature was kept at 80 ° C. for 1 hour 30 minutes. The flask was removed from the oil bath and cooled to 30-40 ° C. 2.1 grams of NaBH ₄ was dissolved in methanol 30 mL, and the solution (it took 30 to 45 minutes) was added dropwise to the flask temperature to keep below 50 ° C.. The flask was then placed in an oil bath at 80 ° C. for 1 hour. The methanol was removed by reducing the pressure. A dark red to black sticky syrup was obtained. The mortar test results for the materials are shown in Table 8.

[0108]

[Table 8]

Example 15 Production of Glucose-Hexylamine Adduct 9.0 glucose (50 mM) in a four-necked flask equipped with a mechanical stirrer, a Dean-Stark ^™ trap with condenser, and a dry nitrogen inlet.
Gram samples were melted at 60-80 ° C. with 3.0 grams of acetic acid (50 mM), and 2.0 grams of water. 5.06 grams of hexylamine (50 m
M) was added slowly along with 7 mL of methanol. The temperature was maintained at 65-68 ° C for 2 hours under a slow continuous nitrogen flow. The methanol was removed by rotary evaporation.
A sticky black syrup was obtained. The mortar test procedure was the same as described in Example 10.

Example 16 Preparation of a Corn Syrup Ethanolamine Adduct A 54 gram sample of corn syrup (35% dextrose equivalent) was a 4-neck flask equipped with a mechanical stirrer, Dean-Stark ^™ trap with condenser, and a dry nitrogen inlet. I put it inside. The temperature was increased to 80 ° C. and a 0.38 mL aliquot of 5N aqueous HCl was added to the syrup. 7.0 grams of monoethanolamine were then slowly added to the flask. The solution was kept stirring under a slow stream of nitrogen for an additional hour. A sticky black syrup was obtained. The mortar test results of the materials are shown in Table 9 along with those of the corn syrup.
The mortar test procedure was the same as described in Example 10.

[0111]

[Table 9]

Example 17 Preparation of a hydrogenated corn syrup ethanolamine adduct A 36.6 gram sample of corn syrup (62% dextrose equivalent), 6.4 grams of monoethanolamine were added to a mechanical stirrer, Dean with condenser. -Placed in a 4-neck flask equipped with a Stark ^™ trap and a dry nitrogen inlet. The solution was mixed at room temperature for 20 minutes. Dissolve 1.99 grams of NaBH ₄ in 30 mL of methanol and add the solution to a flask.
It was added dropwise over a period of 5 minutes. The temperature was about 35 ° C. The flask is then 60
C. in an oil bath for an additional hour. The flask was then removed from the oil bath and 40 mL of water was added. A clear golden solution was obtained. The mortar test results for the materials are listed in Table 1 along with those for corn syrup (35% dextrose equivalent).
0 is shown. The mortar test procedure was the same as described in Example 10.

[0113]

[Table 10]

Example 18 Use of Hexyl Gluconamide as Grinding Aid for Cement Cement clinker from Scancem (21.62% SiO ₂ , 3.42% Al ₂ O ₃ , 3.32% Fe ₂ O ₃₎ 00%, CaO 65.15%, MgO 2.64%, S
_{O 3 1.49%, Na 2 O0.23} %, K 2 O1.21%, TiO 2 0.19%, P 2 O 5 0.04%, Mn 2 O 3 0.05%, SrO0.03% , LOI (950 ° C.)
A 3325 g sample of 31%, C3S69, C2S10C3A4, C4AF9) was combined with 175 g of Terra Alba gypsum and 2.8 g of hexylgluconamide. These materials were placed in a rotary ball mill and ground.
Blaine surface area (BSA) was measured periodically as described in ASTM C204. This procedure was repeated for control samples.

[0115]

[Table 11]

The flow distance of the mortar (6% water content) was tested. The mortar test process is Example 1
The same as described in No. 0. The day 3 strength of the cured sample of this mortar was tested according to the procedure preceding ASTM C109.

[0117]

[Table 12]

Example 19 Calcium Carbonate Sedimentation Experiment A sedimentation experiment for producing a diluted suspension of calcium carbonate powder (about 0.079% by volume) was performed. (CaCO ₃ powder from Aldrich, average diameter of 10 microns)
. Small amounts of N-pentylgluconamide (preparation was similar to that of Example 9)
Was administered into the suspension (0.75-1.60 based on calcium carbonate powder).
weight%). The suspension was treated for exactly 5 minutes by ultrasonic exposure and then redispersed by stirring. The suspension was then quickly transferred to a large capped cylinder and left for sedimentation observation. Sedimentation was measured after 20 minutes and the powder volume fraction during precipitation was calculated. The higher powder volume fraction during precipitation was denser, which indicated better dispersion of the powder.

The sedimentation results are shown in Table 13 below. N-pentylgluconamide had a higher powder volume fraction in the final precipitate, indicating that the compound had the ability to disperse the powder.

[0120]

[Table 13]

Example 20 Preparation of Methyl N-Methyl Gluconamide A dry round bottom flask charged with 3.85 g of NaHCO ₃ and a magnetic stir bar was charged with 1
00 ml of anhydrous THF and 5 ml of butyric anhydride were added. N-methylglucamine (6 g) was added in small portions in solid form. After the addition was complete, the mixture was stirred for a further 5 minutes. A heavy white precipitate formed upon dropwise addition of 1 ml of methanol. The mixture was stirred for 2 hours. Additional ethanol (30 ml) was added and the mixture was stirred for 30 minutes. A white solid was filtered off. The clear filtrate was concentrated on a rotary evaporator. Acetone (15 ml) was added to the clear liquid. Upon gentle heating of the solution, a white precipitate suddenly formed. The white solid was washed with acetone and dried under vacuum.

[0122]

[Table 14]

The above examples are provided for illustrative purposes only and do not limit the scope of the invention.

[Brief description of the drawings]

The following detailed description of the preferred embodiments of the present invention, together with the accompanying drawings, will assist in understanding the various advantages and features of the present invention.

FIG. 1 is a graphical illustration of the flow performance of a cement composition comprising various admixtures including the admixture of the present invention.

FIG. 2 is a graphical illustration of the cure retarding performance of a cement composition comprising various admixtures including the admixture of the present invention.

FIG. 3 is a diagram of an exemplary evaporation method of the present invention for producing the sugar amide composition of the present invention.

FIG. 4 is a diagram of a preferred crystallization method of the present invention for producing the sugar amide composition of the present invention.

FIG. 5 is a diagram of a preferred extraction method of the present invention for producing the sugar amide composition of the present invention.

FIG. 6 is a diagram of a preferred solvent replacement method of the present invention for producing the sugar amide composition of the present invention.

FIG. 7 is a diagram of another preferred solvent replacement method of the present invention for producing the sugar amide composition of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 24/38 C04B 24/38 Z 28/02 28/02 // C04B 103: 40 103: 40 (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW 122 (72) Inventor Williams, Cyon, 1970, Massachusetts, United States 01970 Selem Bisteria Street 12 Apartment 1 (72) Inventor Jiyaki Moyitsu, Ferek, Masashi, United States Clark, Ginebla, United States 02465, Massachusetts, U.S.A. 02465, Newton River Street, 169 Number 1 (72) Inventor Seth, Jyotei 0810, Andrew Elysian Drive, Massachusetts, U.S.A. (72) Inventor Westgate, Paul 01460 Littleton Nashiyoba Road, Massachusetts, United States 83 (72) Inventor Williams, Brent 02139, Cambridge, Massachusetts, United States 02139 Cambridge Apartments 1 Franklin Street 197 (72) Inventor Roberts, Lawrence Earl 01720 Acton, Windsor Avenue, Massachusetts, USA 44 F term (reference) 4D077 AB20 AC05 BA03 DC02X DC02Y DC04X DC04Y DC10Y DC12Y DC17X DC17Y DC26Y DC38Y DC42Y DC48Y DC49Y DD08Y DD09Y DD32Y DD33Y DD63Y D E02Y DE04Y DE07Y DE08Y DE13Y DE17Y DE24Y 4G012 PA04 PB17 PB19 PB20 PB36 PB39 PC01

Claims (67)

[Claims] 1. A composition comprising a plurality of particles to be dispersed and a compound for dispersing the plurality of particles, wherein the compound is (A) at least one group of a sugar or a sugar derivative, (B) at least one non-sugar substituent and (C)
A linking group comprising an amide, amine, imide, urea, or mixture thereof for linking the sugar group of component (A) to the non-sugar substituent of component (B).
Composition. 2. The composition of claim 1, wherein said plurality of particles to be dispersed comprise at least one hydratable binder. 3. The composition of claim 2, wherein said hydratable binder comprises Portland cement, limestone, hydrated lime, fly ash, blast furnace slag, volcanic ash, silica fume, or a mixture thereof. 4. The composition of claim 3 wherein said hydratable binder comprises Portland cement. 5. The composition, further comprising Portland cement, further comprises a hydratable binder selected from limestone, hydrated lime, fly ash, blast furnace slag, volcanic ash, silica fume. 5. The composition of claim 4, wherein 6. The composition of claim 2, wherein said plurality of particles to be dispersed comprise a non-hydratable mineral. 7. The composition of claim 1 wherein said sugar group of said compound is derived from a hydroxycarboxylic acid or a salt thereof. 8. The compound according to claim 8, wherein the sugar group comprises aldonic acid or a lactone or salt thereof, aldonic acid or a lactone or salt thereof, uronic acid or a lactone or salt thereof, aldose, ketose, or a mixture thereof. The composition of claim 1 derived from 9. In the compound, the sugar group is gluconic acid (or a salt or lactone), heptogluonic acid (or a salt or lactone).
Or a composition derived from an aldonic acid selected from the group consisting of: 10. The composition of claim 8, wherein in the compound, the sugar group is derived from an aldaric acid selected from glucaric acid or a lactone or salt thereof, heptoglucaric acid or a lactone or salt thereof, or a mixture thereof. 11. The composition of claim 8, wherein in said compound said sugar group is derived from a uronic acid selected from glucuronic acid or a lactone or salt thereof, heptoglucuronic acid or a lactone or salt thereof. 12. The composition of claim 9, wherein said sugar group is derived from an aldose or ketose sugar selected from a glucose sugar, an aldohexose sugar, a sucrose sugar, a tetrose sugar, a pentose sugar, or a mixture thereof. object. 13. The composition of claim 8, wherein in said compound said sugar groups are derived from corn syrup, molasses, or an oxidized form thereof. 14. The composition of claim 8, wherein in the compound, the sugar group is derived from a polyhydroxy alcohol selected from glucitol, sorbitol, mannitol, reduced corn syrup, or a mixture thereof. 15. The composition of claim 1, wherein said non-sugar substituent in said compound is substituted or unsubstituted. 16. The compound of claim 1, wherein the non-sugar substituent comprises an oxyalkylene group, a hydroxy group, an amino acid group, a sulfonate group, a phosphonate group, or at least one alkyl having a mixture thereof. Fifteen
Composition. 17. In the compound, the sugar group is a C ₅ -C ₇ sugar acid derivative,
The linking group is an amide and the non-sugar substituent is at least one (AO) _n-
R ¹ oxyalkylene group [where AO represents a C ₂ -C ₃ alkoxyl group, R ¹ represents hydrogen or a C ₁ -C ₃ alkyl group, and “n” represents an integer of 1 to 100]
The composition of claim 1, wherein the composition is: 18. The composition of claim 1, wherein in said compound, said non-sugar substituent comprises at least two alkyl, aryl, or alkylaryl groups attached to said linking group. 19. The non-sugar substituent, wherein the at least two alkyls are
19. The composition of claim 18, wherein an aryl or alkylaryl group is linked to said linking group by at least one oxyalkylene group. 20. The composition of claim 19, wherein each of said at least one oxyalkylene group comprises an ethylene oxide and a propylene oxide group. 21. the compound structural formula _{[G] g [X] x} [Q] q [ wherein, G represents at least one group of the sugar or sugar derivative, "g" is 1 to 10
X is an integer of 0, X represents a bonding group selected from amide, amine, imide, urea, or a mixture thereof, “x” is an integer of 1 to 100, and Q is an alkyl, aryl or alkylaryl group. , A non-sugar substituent selected from an oxyalkylene oligomer or polymer group, a polyoxyalkylene oligomer or polymer group, or a mixture thereof, and "q" is an integer from 1 to 100]. Item 10. The composition according to Item 1. 22. In the compound, “g” is 1 to 50, X is an amide, “x” is less than or equal to “q”, and Q is one substitution per sugar group. An alkyl group having a substituted or unsubstituted C ₁ -C ₈ alkyl group, or one substituted or unsubstituted C ₆ per sugar group
-C ₈ aryl or alkylaryl group having an aryl or alkyl aryl group or a non-selected from oxyalkylene or polyoxyalkylene oligomer or polymer group having a repeating ethylene oxide and propylene oxide groups, - represents a sugar substituent, wherein 22. The composition of claim 21, wherein the number of repeating units is 2-200, and "q" is an integer from 1 to 100. 23. The compound represented by the general formula: Wherein G ¹ represents a monomeric sugar group after amidation of reacting a sugar acid with a non-sugar amine, and G ¹ is linear or cyclic in form, and AO is C ₂ -C ₄ alkoxyl, R ¹ and R ² represents hydrogen or C ₁ -C ₃ alkyl groups independently "n" and "p"
Each independently represents an integer from 0 to 100, and the sum of “n” and “p” is 1
And R ³ and R ⁴ independently represent hydrogen or a C ₁ -C ₈ alkyl group, an alkylaryl group, or an aryl ring. 24. The composition of claim 23 wherein said C ₂ -C ₄ alkoxyl group comprises ethylene oxide and propylene oxide groups. 25. The composition of claim 24, wherein at least one of said R ¹ , R ² , R ³ , and R ⁴ groups contains at least one substituted group. 26. A said compound, said "[G]" is comprises a C ₅ -C ₇ sugar acid or a derivative of a salt thereof, X is an amine, and Q is at least one (A
O) comprises a _n -R oxyalkylene group, wherein AO represents C ₂ -C ₃ alkoxy radical, R represents hydrogen or C ₁ -C ₃ alkyl or C ₇ -C ₂₀ aryl group, and 22. The composition of claim 21, wherein "n" represents an integer from 1 to 100. 27. The composition of claim 1, wherein said composition is in the form of a dry powder. 28. The composition of claim 1, wherein said binder is cement and said composition further comprises fine aggregate. 29. The composition of claim 28, wherein said composition further comprises coarse aggregate. 30. The composition of claim 1, further comprising water. 31. The particles comprising: (A) at least one group of a sugar or a sugar derivative;
(B) at least one non-sugar substituent, and (C) the sugar group of component (A) as a component (
B) modifying a particle-containing composition comprising combining with a compound comprising a linking group comprising an amide, amine, imide, urea, or mixture thereof for attachment to a non-sugar substituent. How to qualify. 32. In the compound, the at least one non-sugar substituent is of the formula
(AO) _n -R wherein AO represents a C ₂ -C ₃ alkoxyl group, and R represents hydrogen or a C ₁ -C ₃ alkyl group, and “n” represents an integer from 1 to 100. 32. The method of claim 31, comprising a group having the formula: 33. The method of claim 31, wherein said particles are cement, and said compound is combined with said cement during or after manufacture of said cement. 34. The method of claim 33, wherein said compound is combined with said cement in an amount of 0.005 to 0.5% by weight, based on the weight of said cement. 35. The reaction of a sugar group with an amine or diamine to react (A) at least one group of a sugar or sugar derivative, (B) at least one non-sugar substituent, and (C) component (A). Comprising providing a compound comprising a linking group comprising an amide, amine, imide, urea, or mixture thereof for linking the sugar group of formula (I) to the non-sugar substituent of component (B). For producing a compound for dispersing a compound in an aqueous environment. 36. A sugar mixture, an amine, and a solvent are introduced into a mixing vessel to produce a reaction mixture, produce a sugar amide reaction product, and separate the sugar amide reaction product from the reaction mixture solvent. A method for producing a sugar amide derivative, comprising: 37. The method of claim 36, wherein said sugar derivative comprises a sugar or a salt thereof or a sugar acid derivative of a lactone thereof. 38. The method of claim 36, wherein said amine comprises a primary amine, a secondary amine, or a mixture thereof. 39. The amine is substituted with a group selected from aromatic, hydroxy, ether, halogen, unsaturated alkyl, carbonyl, ester, amino, nitro, carboxylic acid, nitrilo, thio, or sulfone functionality. 37. The method of claim 36. 40. The method of claim 36, wherein said solvent comprises an alcohol, a polar organic solvent, an aromatic hydrocarbon, an amine, or a mixture thereof. 41. The method of claim 36, wherein said solvent comprises a polar organic solvent, a chlorinated hydrocarbon, an ether, an amide, a nitrile, or a mixture thereof. 42. The method of claim 40, wherein said solvent comprises an amine solvent having a tertiary amine. 43. The method of claim 36, wherein said mixing tank is a batch mixing tank or an in-line tank. 44. The method of claim 43, wherein said mixing vessel is an in-line vessel. 45. The method of claim 36, wherein said separating step is performed by evaporating said reaction mixture solvent. 46. The method of claim 36, wherein said separating step further comprises heating said reaction mixture to a temperature below the carbonization temperature of said sugar amide derivative. 47. The method of claim 36, further comprising reducing pressure on said reaction mixture, thereby removing solvent from said sugar amide product. 48. The method of claim 36, further comprising removing a solvent from said sugar amide reaction product by flowing a gas over or through said reaction mixture. 49. The method of claim 36, wherein in said separating step said sugar amide reaction product forms a precipitate. 50. The method of claim 36, comprising cooling the sugar amide reaction product in the reaction mixture solvent to precipitate the reaction product from the reaction mixture solvent. 51. The method of claim 36, further comprising filtering the reaction mixture solvent to remove the sugar amide reaction product. 52. The method of claim 36, wherein said separating step comprises extracting the reaction product from a solvent with water. 53. The separating step comprises flowing the sugar amide reaction product and solvent in a first flow direction and flowing water in a second flow direction countercurrent to the first flow direction. 48. The method of claim 47, comprising. 54. The method of claim 36, wherein said solvent comprises toluene, anisole, benzene, acetonitrile, xylene, methyl butyl ether, or a mixture thereof. 55. The method of claim 54, wherein said solvent comprises toluene or xylene or xylenes. 56. The method of claim 36, further comprising flowing water and at least one buffer in a second flow direction that is countercurrent to said first flow direction. 57. The method of claim 36, wherein after said step of producing a sugar amide reaction product, said step of separating said sugar amide reaction product from said reaction mixture solvent comprises replacing the solvent with water. 58. The step of replacing the solvent with water introduces water into the mixing vessel;
37. The method of claim 36, wherein the sugar amide reaction product in aqueous form is removed from the mixing vessel and a distillation column connected to the mixing vessel is used. 59. The method of claim 58, further comprising condensing and refluxing the solvent after distillation. 60. The method of claim 59, further comprising returning distilled solvent to said mixing vessel. 61. The solvent displacement step provides a continuous in-line mixing vessel for combining the amine compound, the sugar derivative component, and the solvent together to obtain a sugar amide reaction product in a solvent. 37. The method of claim 36, comprising flowing the reaction product of Claim 1 through a distillation column. 62. The method of claim 57, further comprising heating water to generate steam in said distillation column. 63. The method of claim 57 wherein a solvent is separated from said reaction product and reused in said solvent displacement step. 64. The method of claim 36, wherein a solvent comprising an amine is used. 65. (A) at least one group of a sugar or sugar derivative, (B) at least one non-sugar substituent, and (C) a saccharide group of component (A) as a non-sugar of component (B). A compound for modifying a particle-containing composition comprising a binding group comprising an amide, amine, imide, urea, or a mixture thereof for binding to a substituent. 66. The method wherein the at least one non-sugar substituent is an oxyalkylene or polyoxyalkylene oligomer or polymer group (eg, preferably a repeating C ₂ -C ₄ oxyalkylene group, or more preferably, a repeating ethylene oxide and Having a propylene oxide group, wherein the number of repeating units is 2-20
65. The compound of claim 65, wherein 67. (A) at least one group of a sugar or sugar derivative, (B) at least one non-sugar substituent, and (C) a sugar group of component (A) as a non-sugar of component (B). A non-hydratable solid comprising introducing a compound comprising a linking group comprising an amide, amine, imide, urea, or a mixture thereof for attaching to a substituent to the non-hydratable solid Is dispersed in an aqueous system.