WO2001076729A2

WO2001076729A2 - Defoamer compositions and uses therefor

Info

Publication number: WO2001076729A2
Application number: PCT/US2001/011142
Authority: WO
Inventors: George A. Smith
Original assignee: Huntsman Petrochemical Corporation
Priority date: 2000-04-06
Filing date: 2001-04-06
Publication date: 2001-10-18
Also published as: WO2001076729A3; AU2001253179A1

Abstract

Anionic surfactant compositions containing one or more multi-functional polyetheramines as foam suppressant/s. The compositions may be formulated with one or more anionic surfactants such as alkylbenzene sulfonates, and may be optionally adsorbed onto a solid carrier, such as a magnesium silicate material.

Description

DEFOAMER COMPOSITIONS AND USES THEREFOR

Applicant: Huntsman Petrochemical Corporation Inventor: George A. Smith

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to surfactant compositions, and more particularly to anionic surfactant compositions containing one or more multi-functional polyether amines as foam suppressant s.

2. Description of Related Art

The word "surfactant" is derived from the words "surface active agent". Within the definition of this word are included various soaps, detergents, emulsifiers, wetting agents, and dispersants. Among other things, surfactants are known for their ability to make water and oil miscible with one another, and this ability is attributed to the property of surfactants in general to form micellular domains owing to the presence of a hydrophobic and hydrophilic portion within the same given surfactant molecule. When surfactants are in a solution, they tend to collect at the surface of the solution, reducing the free energy of the surface, which makes it easier for the solution to spread across a solid. Thus, a further property of surfactants is that they facilitate the wetting of solid surfaces by solutions. Since the presence of both hydrophobic and hydrophilic portions within the same molecule may be accomplished in any one of several ways, and since surfactant molecules may be substituted with various alkyl, aryl, inorganic, or other chemical groups or combinations thereof, products available in the marketplace which fall under the classification of surfactant are numerous.

One property common to surfactant solutions is the tendency to generate foam (e.g., soap bubbles), especially with agitation. In some situations, it may be desirable to reduce, suppress or eliminate such foams. For example, the introduction of high efficiency washing machines in North America is changing the traditional requirements for laundry detergents. Not only is it desirable for detergent to remove soils and stains from fabric, but also desirable is the property of low foaming to prevent suds lock or foam expulsion from the machine. Specifically, traditional vertical-axis clothing washing machines are now being replaced by horizontal-axis machines, similar to those in widespread use throughout various European States. Typically, such horizontal-axis machines supply more mechanical agitation to the contents of the rotating drum, which results in a greater degree of foam being generated. The larger foam volumes require more effective foam suppression or control. In conventional powder detergents, foam control is typically achieved by adding a defoamer or anti-foaming agent to the formulation.

Other applications in which foam generation is undesirable include, but not limited to, high speed coating operations where foam is detrimental to coating appearance, and in bottle wash and auto dish applications where foam generation tends to decrease cleaning efficiency and causes water spots.

One type of conventional defoamer is typically present as a coating on particles of soda ash (sodium carbonate) at, for example, a level of between about 5% to 10%. Such materials are free flowing powders, which may be dry blended into various powdered detergent formulations. Examples of such defoaming materials include silicon-based defoamers on inorganic carriers for use with powdered detergents. Drawbacks to these conventional materials include high costs and potential wetting and leveling problems in coating applications.

Furthermore, although conventional defoamers may achieve some foam suppression effectiveness when used with powdered detergents, they are typically not suitable for use with liquid detergents. Therefore, for liquid detergents foam suppression may be difficult to achieve. In the past, soap has been employed as a defoamer for liquid laundry detergents. In this capacity, the soap interacts with hard water ions to form insoluble particles which tend to suppress foam generation. However, because its defoaming capability relies on hard water ions, soap tends to not work well in soft water situations. Silicon-based defoamers have also been used in liquid systems but they tend to have compatibility problems and tend to lose efficacy over time due to solubilization in surfactant micelles.

SUMMARY OF THE INVENTION

Disclosed are surfactant compositions including multifunctional polyether amines which are effective as defoamers in laundry detergent formulations that include anionic surfactants. Advantageously, the disclosed multifunctional polyether amine foam suppressants may be employed with both powder and liquid laundry detergent formulations, and are effective regardless of water hardness, thus providing an attractive alternative to soap defoamers which are typically employed with liquid laundry detergents.

Advantageously, the disclosed multifunctional polyether amine foam suppressants may be employed to suppress or eliminate foam in a variety of aqueous surfactant systems containing anionic surfactants. With benefit of this disclosure, those of skill in the art will understand that examples of surfactant systems with which the disclosed foam suppressants may be employed include, but are not limited to, aqueous surfactant systems known in the art such as low foam laundry detergents (including high efficiency laundry formulations), bottle wash formulations, auto dish formulations, high speed coating operation formulations, etc. Furthermore, the disclosed multifunctional polyether amine foam suppressants may be employed in solid surfactant compositions (e.g., powdered laundry detergents), absorbing a multifunctional polyether amine on a solid carrier, such as magnesium silicate.

In various embodiments, the disclosed foam suppressants may offer additional advantages, such as the ability to formulate a 100% active liquid composition that requires no water and therefore offers savings in weight, space and cost associated with transportation. In one laundering application embodiment, the disclosed foam suppressants may offer anti- redeposition properties and/or act to stabilize and disperse soil particles. In another embodiment, the disclose foam suppressants may provide dye transfer inhibition properties which may prevent bleeding or transfer of colored dyes from one laundry item to another. The foregoing is only a partial list of possible benefits and advantages that may be offered by the disclosed foam suppressant compositions.

In one embodiment, the disclosed foam suppressants may be employed in surfactant systems (such as laundry formulations) that have an alkaline pH, for example, a pH of from about 7 to about 9 for enzymatic formulations, and a pH of from about 8 to about 12, alternatively from about 8 to about 11, further alternatively of about 10, for non-enzymatic built liquids. However, it will be understood that these pH ranges are exemplary only, and that the disclosed foam suppressants may be employed with surfactant compositions having pH values outside these ranges as well.

In yet another embodiment, foam suppressants may be formulated from polyether amines that do not contain alkyl groups synthesized from alcohols. Advantageously, this means that the cost of foam suppressants of this embodiment are not tied to alcohol prices and availability. Furthermore, such polyether amine molecules may remain substantially unassociated in solution, i.e., they form substantially no micelles in solution. This feature tends to allow the formulation of more effective foam suppressants at lower use concentrations.

In one respect, disclosed is a composition, including: at least one anionic surfactant; and at least one multifunctional polyetheramine including at least two amine groups per molecule, and having a molecular weight of at least about 1000; wherein each of the amine groups is a secondary amine group, or a tertiary amine group; and wherein none of the substituent groups attached to a nitrogen atom of the multifunctional polyetheramine is an n- propyl group or radical, or an alkyl group or radical having more than four carbon atoms.

In another respect, disclosed is a liquid surfactant composition, including: at least one anionic surfactant; at least one multifunctional polyetheramine, the multifunctional polyetheramine including two or three amine groups per molecule, and having a molecular weight of from about 1000 to about 10,000; and solvent; wherein the multifunctional polyetheramine is present in the composition in an amount effective to suppress foam in the composition when the composition is combined with water; and wherein the multifunctional polyetheramine includes a di-functional amine of the formula:

in which: x may be from about 25 to about 100;

R, may be one of H, (CH₂CH₂O)_nι-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ may be one of H, (CH₂CH₂O)_n2-H, or (CH₂CH(CH₃)0)_π2-H;

R₃ may be one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)0)„₃-H; R4 may be one of H, (CH₂CH₂O)„₄-H, or (CH₂CH(CH₃)O)_n4-H;

and each of nl, n2, n3, and n4 may be independently from about 1 to 20; or

wherein the multifunctional polyetheramine includes a di-functional amine of the formula:

in which: b may be from about 5 to about 50, and a+c may be from about 2 to about 20;

Ri may be one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ may be one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ may be one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R4 may be one of H, (CH₂CH₂0)_n -H, or (CH₂CH(CH₃)0)_n4-H;

and each of nl, n2, n3 and n4 may be independently from about 1 to

20; or

wherein the multifunctional polyetheramine includes a tri-functional amine of the formula:

where: x+y+z may be from about 5 to about 100;

Ri may be one of H, (CH₂CH₂0)_n*-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ may be one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ may be one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R4 may be one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)O)_n4-H;

R₅ may be one of H, (CH₂CH₂O)_n5-H, or (CH₂CH(CH₃)O)_n5-H;

Re may be one of H, (CH₂CH₂0)_n6-H, or (CH₂CH(CH₃)0)_n6-H;

and each of nl, n2, n3, n4, n5 and n6 may be independently from about 1 to 20; or

CH, CH,

,^Rι

CH— O— (-CH— CH₂— θ )-( CH— CH — O-)— CH₂— CH — N

R,

CH, CH,

R3

CH — O— ( CH₂— CH₂— θ )-( CH— CH — θ ) CH, CH —

R„

CH, CH,

R_e

CH— O— ( CH₂— CH— θ )-( cH₂— -CH — O-)— CH_j— CH — N

R,

in which: x+y+z equals from about 3 to about 100;

a+b+c equals from about 3 to about 30;

R, may be one of H, (CH₂CH₂O)_nι-H, or (CH₂CH(CH₃)0)_n]-H;

R₂ may be one of H, (CH₂CH₂O)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ may be one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R> may be one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)0)_n -H;

R₅ may be one of H, (CH₂CH₂O)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re may be one of H, (CH₂CH₂O)_n6-H, or (CH₂CH(CH₃)0)_n6-H;

and each of nl, n2, n3, n4, n5 and n6 may be independently from about 1 to 20; or a mixture thereof. In another respect, disclosed is a composition including at least one multi-functional polyetheramine adsorbed onto the surface of particles of solid carrier; the multi-functional polyetheramine having a molecular weight of at least about 1000.

In another respect, disclose is a method of suppressing foam in an aqueous surfactant system, including combining a multi-functional polyetheramine with the aqueous surfactant solution; wherein the aqueous surfactant system includes at least one anionic surfactant; wherein the multi-functional polyetheramine includes at least two amine groups per molecule, and has a molecular weight of at least about 1000; wherein each of the amine groups is a primary amine group, a secondary amine group, or a tertiary amine group; wherein each tertiary amine group present includes a nitrogen atom bound to three adjacent substituent groups, each of the adjacent substituent groups being (CH₂CH₂O)-H or (CH₂CH(CH₃)O)-H; and wherein the multi-functional polyetheramine is present in an amount to suppress foam in the surfactant solution when the solution is combined with water.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows foam height as a function of concentration of multifunctional polyether amine in a surfactant composition according to one embodiment of the disclosed compositions and methods.

FIG. 2 shows foam height comparison for surfactant compositions containing a variety of polyether amines

FIG. 3 shows foam height as a function of concentration of multifunctional polyether amines in a surfactant composition according to two embodiments of the disclosed compositions and methods.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

As used herein, the indefinite articles "a" and "an" connote "one or more."

In the formulation of the disclosed surfactant compositions, multifunctional polyether amines may be added to or otherwise combined with a surfactant systems including at least one anionic surfactant. Suitable multifunctional polyether amines include any polyether amine having at least two amine groups per molecule, and having a molecular weight sufficiently high enough to reduce or eliminate foam formation, for example, as compared to the same surfactant solution absent one or more of the disclosed multifunctional polyether amines. W ile not wishing to be bound by theory, it is believed that amine groups of multifunctional polyether amines are capable of neutralizing charged head groups in an anionic surfactant, forming a salt and effectively coupling the anionic surfactant to the polyether amine molecule. A possible mechanism for the interaction between a difimctional polyether amine (in this embodiment, a "JEFF AMINE ED®" compound having two primary amine groups, available from Huntsman Corporation, and described further herein) and a linear alkyl benzene sulfonate is illustrated below.

Among the variables which may affect the foam suppression effectiveness of a multifunctional polyether amine are molecular weight, hydroprobicity and functionality. As illustrated in Example 2, favorable foam suppression characteristics may be achieved using multifunctional species, suggesting that two or more anionic surfactant molecules are bound by multifunctional polyether amines to suppress the foam. Furthermore, the data from Example 2 also suggests that foam suppression characteristics tend to increase with increasing molecular weight and increasing hydroprobicity of a multifunctional polyether amine molecule. This suggests that the polyether amine surfactant complex may form small hydrophobic particles at the air/water interface which serve to suppress the foam.

Suitable multifunctional polyether amines include polyether amines having two or more amine groups per molecule. Suitable amine groups include primary, secondary and tertiary amine groups, as well as mixtures thereof. Specific examples of suitable polyether amines include, but are not limited to, difimctional and trifunctional polyether amines having two or three primary amine groups per molecule, respectively. Suitable multifunctional polyether amines may have polyether blocks comprised of alkylene oxide-based groups, wherein each group has a carbon count of from about 2 to about 5. The multifunctional polyether amines may be comprised of individual polyether blocks having the same number of carbon atoms and structure, or alternatively may be composed of individual polyether groups having differing carbon counts and/or isomeric structure.

Suitable polyether blocks for polyetheramine include, for example, polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly (1,2-butylene glycol), and poly (tetramethylene glycol). Glycols may be aminated using well-known methods to produce the polyetheramines. For example, glycols may be prepared from ethylene oxide, propylene oxide or combinations thereof using methods such as methoxy or hydroxy initiated reaction. When both ethylene oxide and propylene oxide are used, the oxides can be reacted simultaneously when a random polyether is desired, or reacted sequentially when a block polyether is desired.

In one embodiment, polyetheramines may be prepared from ethylene oxide, propylene oxide or combinations thereof. For example, when a polyetheramine is prepared from ethylene oxide, propylene oxide or combinations thereof, the amount of ethylene oxide on a molar basis may range from about 0 to about 100% of the polyetheramine. Polyols and amines, including polyalkylene polyamines and alkanol amines or any amine that is not a polyetheramine as disclosed herein, may be absent from the composition. Similarly, functional groups other than ether linkages and amine groups may be absent from a polyetheramine.

Suitable polyetheramines may be prepared, for example, using amination techniques such as described in United States Patent Nos. 3,654,370; 4,152,353; 4,618,717; 4,766,245; 4,960,942; 4,973,761; 5,003,107; 5,352,835; 5,422,042; and 5,457,147, each of which is incorporated herein by reference. In one exemplary embodiment, polyetheramines may be made by aminating a polyol, such as a polyether polyol with ammonia in the presence of a catalyst such as a nickel-containing catalyst (e.g., Ni/Cu/Cr catalyst, etc.).

In one embodiment, multifunctional polyether amine foam suppressants include those polyether amines having two or more amines per molecule, and having a molecular weight sufficiently high to be effective to suppress foam formation in a surfactant composition when present in an effective amount. In one embodiment, such multifunctional polyether amines may have a molecular weight of at least about 1000, alternatively of at least about 1500, and alternatively of at least about 2000. In another embodiment, suitable multifunctional polyether amines include, but are not limited to, diamines and triamines having a molecular weight of from about 1000 to about 10,000, alternatively from about 1500 to about 10,000, alternatively from about 2000 to about 10,000, alternatively from about 1000 to about 7500, alternatively from about 1500 to about 7500, alternatively from about 2000 to about 7500, alternatively from about 1000 to about 5000, alternatively from about 1500 to about 5000, alternatively from about 2000 to about 5000, alternatively from about 1000 to about 4000, alternatively from about 1500 to about 4000, alternatively from about 2000 to about 4000.

In separate respective and alternative embodiments, multifunctional polyether amines having a molecular weight in a range of from about A to about B may be employed, where for each respective embodiment the value of A may be selected from the range of whole number values of from about 1000 to about 2000, and a corresponding value of B may be selected from the range of whole number values of from about 5000 to about 10,000. For example, in an embodiment where A = 1050 and B = 6500, a multifunctional polyether amine having a molecular weight of from about 1050 to about 6500 would be represented. In yet another embodiment, multifunctional polyether amines having a molecular weight in a range of greater than about A may be employed, where the value of A may be selected from the range of whole number values of from about 1000 to about 2000.

In another embodiment, each of said amine groups of a multifunctional polyetheramine is a primary amine group, a secondary amine group, or a tertiary amine group; with the provision that each tertiary amine group present comprises a nitrogen atom bound to three adjacent substituent groups that are each (CH₂CH₂0)-H or (CH₂CH(CH₃)0)- H. In one embodiment, these materials may be used in their nonionic form at pH values above the pKa, or in their cationic form at pH values below their pKa. In yet another embodiment, none of the substituent groups attached to a nitrogen atom of a multifunctional polyetheramine is an w-propyl group (or radical), or an alkyl group (or radical) having more than four carbon atoms. Specific examples of suitable difimctional polyether amines include, but are not limited to, "JEFFAMINE D®" di-functional difimctional amines, available from Huntsman Corporation (including alkoxylated derivatives thereof), and having the following structure ("Structure A"):

where: ^•x is from about 25 to about 100;

Ri is one of H, (CH₂CH₂O)_nι-H, or (CH₂CH(CH₃)O)„ι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R4 is one of H, (CH₂CH₂0)„₄-H, or (CH₂CH(CH₃)O)_n4-H;

each of nl, n2, n3 and n4 may be independently from about 1 to 20; and

wherein the combination of selected constituents and constituent values (i.e., x, Ri - R₄, and nl - n4) results in a molecule having a molecular weight of at least about 1000, or another suitable molecular weight or molecular weight range as otherwise described herein.

Specific examples of such difunctional amines include, but are not limited to, Jeffamine® D-2000 and D-4000, and mixtures thereof. In the case of Jeffamine® D-2000, x is about 33 and each of Ri, R₂, R₃, and R is H. For Jeffamine® D-4000, x is about 68 and each of Ri, R₂, R₃, and Rt is H. As indicated by the formula above, ethoxylated and propoxylated versions of these exemplary difunctional amines (in which one or more of Rj, R₂, R₃, and R are ethoxy and/or propoxy groups) are also suitable, as are mixtures thereof. In the case of Huntsman "JEFFAMINE®" polyetheramines, a numeric suffix is provided that indicates the weight average molecular weight. An alphabetic designation precedes each numeric suffix, identifying the functionality of the particular compound: "M" for monofunctional, "D" for difunctional, and "T" for trifunctional. The letter "E" (such as in "JEFFAMINE® ED-2000") denotes a predominantly polyethylene oxide backbone. For alkoxylated versions of "JEFFAMINE®" polyetheramines, an additional alphanumeric subscript is provided that indicates moles of alkoxylation, and identity of alkoxy group, respectively. For example, "JEFFAMINE® D-2000-4EO" and "JEFFAMINE® D-4000- 4EO" denote Jeffamine® D-2000 and Jeffamine® D-4000 amine molecules, respectively (as described above), having 4 moles of ethoxylation (i.e., in Structure A each of Rj, R₂, R , and R₄ is (CH₂CH₂O)-H; and each of nl, n2, n3 and n4 has a value of one).

In an alternate embodiment, suitable difunctional polyether amines (and alkoxylated derivatives thereof) having Structure A, may have a value of x that is from about 16 to about 100, with the remaining variables being the same as given above (i.e., values of "R" and "n"). In further separate respective alternative embodiments, difunctional polyether amines (and alkoxylated derivatives thereof) having Structure A, and having a value of x in a range of from about C to about D may be employed, where for each respective embodiment the value of C may be selected from the range of whole number values of from about 16 to about 99, and a corresponding value of D may be selected from the range of whole number values of from about 17 to about 100. It will be understood with benefit of this disclosure by those of skill in the art that value of x be varied to obtain desired molecular weight values and minimum molecular weight values to fit particular requirements and/or applications.

In any given embodiment of Structure A, with benefit of this disclosure those of skill in the art will understand that when one or more of Ri, R₂, R₃, and/or R₄ represent one or more alkoxyl groups, the corresponding value (or minimum value) of x may be adjusted downward accordingly to achieve a given molecular weight (or minimum molecular weight).

Other suitable difunctional polyetheramines include, but are not limited to, "JEFFAMINE ED®" compounds, available from Huntsman Corporation, and having the following structure ("Structure B"): ^Rl ^R3

N-CH — CH₂-(θ-CH — CH₂— )-(-0-CH₂— CH₂-)-(— O-CH— CH-)-N

/ I I a b I ^c \

R_j CH, CH, CH, R,

where: b is from about 5 to about 50, and a+c is from about 2 to about 20;

Ri is one of H, (CH₂CH₂0)„--H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂O)_π2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

RA is one of H, (CH₂CH₂O)_n4-H, or (CH₂CH(CH₃)O)_n -H;

each of nl, n2, n3 and n4 may be independently from about 1 to 20; and

wherein the combination of selected constituents and constituent values results in a molecule having a molecular weight of at least about 1000, or another suitable molecular weight or molecular weight range as otherwise described herein.

Specific examples of these difunctional polyetheramines include, but are not limited to, Jeffamine® ED-2003. In the case of Jeffamine® ED-2003, b is about 38.7, a+c is about 6, and each of Ri, R₂, R , and R₄ is H. For Jeffamine® ED-4000, b is about 86.0, a+c is about 2.5, and each of R-, R₂, R₃, and R₄ is H. For Jeffamine® ED-6000, b is about 132, a+c is about 3.0, and each of Ri, R₂, R , and Ri is H. As indicated by the formula above, ethoxylated and propoxylated versions of these exemplary difunctional polyetheramines (in which one or more of Ri, R₂, R₃, and R» are ethoxy and/or propoxy groups) are also suitable, as are mixtures thereof.

In an alternate embodiment, suitable difunctional polyether amines (and alkoxylated derivatives thereof) having Structure B, may have a value of b that is from about 1 to about 50, and a value of a+c that is from about 2 to about 20, with the remaining variables being the same as given above (i.e., values of "R" and "n"). In further separate respective alternative embodiments, difunctional polyether amines (and alkoxylated derivatives thereof) having Structure B, and having a value of b in a range of from about C to about D, and a value of a+c in a range of from about E to F, may be employed, where for each respective embodiment the value of C may be selected from the range of whole number values of from about 1 to about 49, and a corresponding value of D may be selected from the range of whole number values of from about 2 to about 50; and a value of E may be selected from the range of whole number values of from about 2 to about 19, and a corresponding value of F may be selected from the range of whole number values of from about 3 to about 20. It will be understood with benefit of this disclosure by those of skill in the art that values of b and a+c may be varied to obtain desired molecular weight values and minimum molecular weight values to fit particular requirements and/or applications.

In any given embodiment of Structure B, with benefit of this disclosure those of skill in the art will also understand that values of a, b and c may be selectively and independently varied to achieve desired molecular weight and/or foam suppressant properties. For example, to obtain a molecular weight of at least about 1000 when each of Ri, R₂, R₃, and P^ are H, then the value of b may be from about 1 to about 50, and the corresponding value of a+c from about 15 to about 20. Similarly, for a molecular weight of at least about 1000 and all R's = H, when the value of a+c is from about 2 to about 20, the value of b may be from about 18 to about 50. Further, it will be understood that when one or more of Ri, R₂, R₃, and/or R» represent one or more alkoxyl groups, the corresponding values (or minimum values) of b and/or a+c may be adjusted downward accordingly to achieve a given molecular weight (or minimum molecular weight).

Specific examples of suitable trifunctional polyether amines include, but are not limited to, "JEFFAMINE® T" compounds, available from Huntsman Corporation, and having the following structure ("Structure C"):

where: x+y+z is from about 5 to about 100;

Ri is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)0)_ni-H

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H

R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)„₃-H

R₄ is one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)0)_n -H:

R₅ is one of H, (CH₂CH₂0)_n5-H, or (CH₂CH(CH₃)0)_n5-H:

Re is one of H, (CH₂CH₂O)_ne-H, or (CH₂CH(CH₃)0)„₆-H

each of nl, n2, n3, n4, n5 and n6 may be independently from about 1 to 20; and

wherein the combination of selected constituents and constituent values results in a molecule having a molecular weight of at least about 1000, or another suitable molecular weight or molecular weight range as otherwise described herein. Specific examples of these trifunctional amines include, but are not limited to, Jeffamine® T-5000, and ethoxylated and propoxylated version thereof. In the case of Jeffamine® T-3000, x+y+z is about 50, and each of R R₂, R₃, R-., R₅, and Re is H. For Jeffamine® T-5000, x+y+z is about 83, and each of R-, R₂, R₃, Rt, R₅, and Re is H. As indicated by the formula above, ethoxylated and propoxylated versions of these exemplary difunctional polyetheramines (in which one or more of Rj, R₂, R , R₄, R₅, and Re are ethoxy and/or propoxy groups) are also suitable, as are mixtures thereof. For example "JEFFAMINE® T-5000-6EO" denotes an alkoxylated Jeffamine® T-5000 amine molecule (as described above), having 6 moles of ethoxylation (i.e., in Structure C each of Ri, R₂, R , R4, R₅, and Re is (CH₂CH₂O)-H; and each of nl, n2, n3, n4, n5 and n6 has a value of one).

In an alternate embodiment, suitable trifunctional polyether amines (and alkoxylated derivatives thereof) having Structure C, may have a value of x+y+z that is from about 13 to about 100, with the remaining variables being the same as given above (i.e., values of "R" and "n"). In further separate respective alternative embodiments, difunctional polyether amines (and alkoxylated derivatives thereof) having Structure C, and having a value of x+y+z in a range of from about C to about D may be employed, where for each respective embodiment the value of C may be selected from the range of whole number values of from about 13 to about 99, and a corresponding value of D may be selected from the range of whole number values of from about 14 to about 100. It will be understood with benefit of this disclosure by those of skill in the art that values of x+y+z may be varied to obtain desired molecular weight values and minimum molecular weight values to fit particular requirements and/or applications.

In any given embodiment of Structure C, with benefit of this disclosure those of skill in the art will understand when one or more of Ri, R₂, R₃, R₄, R₅, and R₆ represent one or more alkoxyl groups, the corresponding values (or minimum values) of x+y+z may be adjusted downward accordingly to achieve a given molecular weight (or minimum molecular weight).

Other suitable trifunctional polyether amines include, but are not limited to, compounds such as "JEFFAMINE® ET" compounds, formerly available from Huntsman Corporation, and having the following structure ("Structure D"): CH, CH,

R,

CH— O— (-CH₂— CH— θ )-(CH— CH — O-)— CH₂— CH — N

R2

CH, CH,

R,

CH— O — (- CH₂— CH₂— O )-( CH₂— CH — O -)— CH₂— CH — N

R.

CH, CH,

R.

CH₂— O— ("CH₂— CH₂— O-)-( cH— CH — θ )-CH₂— CH — N

R,

where: x+y+z equals from about 3 to about 100;

a+b+c equals from about 3 to about 30;

R, is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)0)_n3-H;

R₄ is one of H, (CH₂CH₂0)_n -H, or (CH₂CH(CH₃)O)_n -H;

R₅ is one of H, (CH₂CH₂0)_n5-H, or (CH₂CH(CH₃)O)„₅-H;

Re is one of H, (CH₂CH₂0)_n6-H, or (CH₂CH(CH₃)O)_n6-H;

each of nl, n2, n3, n4, n5 and n6 may be independently from about 1 to 20; and

Specific examples include Jeffamine® ET-3000, and ethoxylated and propoxylated version thereof. In the case of Jeffamine® ET-3000, x+y+z is about 57, a+b+c is about 4, and each of Ri, R₂, R , R», R₅, and Re is H. As indicated by the formula above, ethoxylated and propoxylated versions of these exemplary difunctional polyetheramines (in which one or more of Ri, R₂, R₃₎ R₄, R₅, and Re are ethoxy and/or propoxy groups) are also suitable, as are mixtures thereof.

In further separate respective alternative embodiments, difunctional polyether amines

(and alkoxylated derivatives thereof) having Structure D, and having a value of x+y+z in a range of from about C to about D, and a value of a+b+c in a range of from about E to F, may be employed, where for each respective embodiment the value of C may be selected from the range of whole number values of from about 3 to about 99, and a corresponding value of D may be selected from the range of whole number values of from about 4 to about 100; and a value of E may be selected from the range of whole number values of from about 3 to about 29, and a corresponding value of F may be selected from the range of whole number values of from about 4 to about 30. It will be understood with benefit of this disclosure by those of skill in the art that values of x+y+z and/or a+b+c may be varied to obtain desired molecular weight values and minimum molecular weight values to fit particular requirements and/or applications.

In any given embodiment of Structure D, with benefit of this disclosure those of skill in the art will understand that appropriate values of x, y and z; and/or a, b and c may be selectively and independently varied to achieve desired molecular weight and/or foam suppressant properties. For example, to obtain a molecular weight of at least about 1000 when each of Ri, R₂, R₃, R_t, R₅, and Re are H, then the value of a+b+c may be from about 3 to about 100, and the corresponding value of x+y+z may be from about 13 to about 20. Similarly, for a molecular weight of at least about 1000 with all R's being H, when the value of a+b+c is from about 10 to about 100, then the corresponding value of x+y+z may be from about 3 to about 20. Further, it will be understood that when one or more of Ri, R₂, R₃, t, R₅, and Re represent one or more alkoxyl groups, the corresponding values (or minimum values) of b and/or a+c may be adjusted downward accordingly to achieve a given molecular weight (or minimum molecular weight).

Other specific examples of suitable multifunctional amines include, but are not limited to, "POLYETHERAMINE D2000," available from BASF; and ethoxylated or propoxylated versions thereof. As shown by the data presented in Example 1 and FIG. 1, foam suppression benefits of the disclosed polyetheramine/anionic surfactant systems may be realized with the presence of even small amounts of a suitable polyetheramine in an aqueous liquid surfactant solution. In one embodiment, amounts as little as about 0.1% may be employed. In another embodiment, polyetheramine is employed in an amount of at least about 0.5% alternatively from about 0.5% to about 10%, alternatively from about 1% to about 10%, and further alternatively from about 1% to about 5% by weight of solution alternatively from about 1% to about 8%, alternatively from about 1% to about 7%, alternatively from about 1% to about 6%, alternatively from about 1% to about 5%, alternatively from about 1% to about 4%, alternatively from about 1% to about 3%, alternatively from about 1% to about 2%, and further alternatively from about 2% to about 10%, alternatively from about 2% to about 9%, alternatively from about 2% to about 8%, alternatively from about 2% to about 7%, alternatively from about 2% to about 6%, alternatively from about 2% to about 5%, alternatively from about 2% to about 4%, alternatively from about 2% to about 3%, alternatively from about 2% to about 2%.

In another embodiment, a surfactant composition may be formulated using components described elsewhere herein so that substantially equivalent molar amounts of amine functionality and surfactant acid functionality are present, so that substantially all of the acid functionality is neutralized.

With benefit of this disclosure, those of skill in the art will understand that suitable anionic surfactants that may be employed in the disclosed compositions and methods include any anionic surfactant known in the art and suitable for detergent or coating applications. In one embodiment, such anionic surfactants may be characterized as having pKa values less than 7. For example, suitable anionic surfactants include, but are not limited to, linear and/or branched chain alkylbenzene sulfonates, alkyl sulfates, ether sulfates, xylene sulfonates, alcohol sulfates, phosphate esters, napthalene sulfonates, secondary alkyl sulfates, α-oleftn sulfonates, phosphate esters, sulfosuccinates, isethionates, carboxylates, betaines, soaps, mixtures thereof, etc. Most of these surfactants are typically sold in the form of a sodium salt, although forms having other cations may be employed, as described below.

In the practice of the disclosed method and compositions, an anionic surfactant, such as alkylbenzene sulfonate, may include any counterion or cation suitable for neutralization. In one embodiment a counterion or cation may be ammonium or substituted ammonium compounds. In this regard, a substituted ammonium may include, but is not limited to, monoethanol ammonium, diethanol ammonium, triethanol ammonium, or a mixture thereof. In another embodiment, such a counterion or cation may be an alkali metal, an alkaline earth metal, or a mixture thereof. Specific examples of alkali metals include, but are not limited to, lithium, sodium, potassium, cesium, or a mixture thereof. Examples of alkaline earth metals include, but are not limited to, magnesium, calcium, strontium, barium, or a mixture thereof.

In one exemplary embodiment, one or more alkylbenzene sulfonate/s may be employed as anionic surfactants. In this regard, alkylbenzene sulfonate compounds having varying molecular weights, alkyl chain length and alkyl chain phenyl location combination may be employed. Examples of such compounds may be found in U.S. Patent No. 3,776,962; U.S. Patent No. 5,152,933; U.S. Patent No. 5,167,872; Drazd, Joseph C. and Wilma Gorman, "Formulating Characteristics of High and Low 2-Phenyl Linear Alkylbenzene Sulfonates in Liquid Detergents," JAOCS, 65(3):398-404, March 1988; Sweeney, W. A. and A. C. Olson, "Performance of Straight-Chain Alkylbenzene Sulfonates (LAS) in Heavy-Duty Detergents," JAOCS, 41:815-822, December 1964.; Drazd, Joseph C, "An Introduction to Light Duty (Dishwashing) Liquids Part I. Raw Materials," Chemical Times & Trends, 29-58, January 1985; Cohen, L. et al, "Influence of 2-Phenyl Alkane and Tetralin Content on Solubility and Viscosity of Linear Alkylbenzene Sulfonate," JAOCS, 72(1):115-122, 1995; Smith, Dewey L., "Impact of Composition on the Performance of Sodium Linear Alkylbenzenesulfonate (NaLAS)," JAOCS, 74(7):837-845, 1997; van Os, N. M. et al, "Alkylarenesulphonates: The Effect of Chemical Structure on Physico-chemical Properties," Tenside Surf. Del, 29(3): 175-189, 1992; Moreno, A. et al, "Influence of Structure and Counterions on Physicochemical Properties of Linear Alkylbenzene Sulfonates," JAOCS, 67(8):547-552, August 1990; Matheson, K. Lee and Ted P. Matson, "Effect of Carbon Chain and Phenyl Isomer Distribution on Use Properties of Linear Alkylbenzene Sulfonate: A Comparison of 'High' and 'Low' 2-Phenyl LAS Homologs," JAOCS, 60(9):1693-1698, September 1983; Cox, Michael F. and Dewey L. Smith, "Effect of LAB composition on LAS Performance," INFORM, 8(l):19-24, January 1997; U.S. Patent Application Serial No. 08/598,692 filed on February 8, 1996, U.S. Patent Application Serial Number 09/141,660 filed on August 28, 1998, and U.S. Patent Application Serial Number 09/143,177 filed on August 28, 1998; all of the foregoing references being incorporated herein by reference in their entirety. Linear alkylbenzene sulfonates ("LAS") are one type of alkylbenzene sulfonate widely used as surfactants in commercial cleanser products because of their effectiveness as detergents, ease of biodegradation, and relative low cost. Linear alkylbenzene sulfonates may be produced via sulfonation of linear alkylbenzene intermediates. Linear alkylbenzene is typically manufactured on an industrial scale using one of two commercial processes which differ from one another primarily by virtue of the catalyst system employed. In this regard, one process employs an aluminum trichloride catalyst, while the other process uses a hydrogen fluoride catalyst. The two processes result in linear alkylbenzene products with different phenyl isomer distributions. For example, a typical phenyl isomer distribution for products of the aluminum trichloride process is about 30% 2-phenyl isomer and about 22% 3- phenyl isomer. In contrast, a typical phenyl isomer distribution for products of the hydrogen fluoride process is about 20% 2-phenyl isomer and about 20% 3-phenyl isomer, although reported values may differ. The product of the aluminum trichloride process, which is relatively high in 2-phenyl isomer content, is often referred to as "high 2-phenyl" linear alkylbenzene, whereas the product of the hydrogen fluoride process, which is relatively low in 2-phenyl isomer content, is often referred to as "low 2-phenyl" linear alkylbenzene.

In one embodiment, alkylbenzene sulfonate compounds used in accordance with the disclosed compositions and methods and having the characteristics described herein include those having a linear alkyl group. Typically linear alkyl chain lengths are between about 8 and about 16 carbon atoms, although greater and lesser lengths are also possible.

One specific low 2-phenyl alkylbenzene sulfonate composition is a sulfonate prepared from a linear alkyl benzene known as "ALKYLATE 225™" (commercially available from Huntsman Specialty Chemicals Corporation). Other examples of suitable linear alkylbenzenes for preparing linear alkyl benzene sulfonates include, but are not limited to, "ALKYLATE 215™", "ALKYLATE 229™", "ALKYLATE H230L™", "ALKYLATE H230H™", and mixtures thereof (also available from Huntsman Specialty Chemicals Corporation). Suitable processes for sulfonating such linear alkyl benzenes include, but are not limited to, those employing an air/S0₃ sulfonator or chlorosulfonic acid.

Specific examples of other types of anionic surfactants include, but are not limited to, the surfactants listed in Table 1 and available from Huntsman Corporation, Houston, Texas. Table 1

Other specific examples of anionic surfactants include, but are not limited to, the surfactants listed in Table 2 available from Witco Corporation, Greenwich, CT.

Table 2

Still other specific examples of anionic surfactants include, but are not limited to, the surfactants listed in Table 3 and available from Stepan Company. Table 3

It will be understood with benefit of this disclosure by those of skill in the art that the preceding examples of anionic surfactants are exemplary only, and that other anionic surfactants meeting criteria set forth herein may also be employed.

With benefit of this disclosure, those of skill in the art will understand that an amount of anionic surfactant employed in the disclosed surfactant compositions may include any amount of anionic surfactant known in the art to be suitable for formulating a surfactant composition, such as a liquid detergent composition, solid surfactant composition, or coating composition In one embodiment, an aqueous liquid surfactant composition may comprise from about 1% to about 30% alternatively from about 5% to about 15% by weight of total weight of the composition of one or more anionic surfactant/s, although greater or lesser amounts are also possible.

Advantageously, the disclosed surfactant compositions may be provided in solid form without a solvent (such as adsorbed on magnesium silicate and/or as a solid which may be combined with a solvent later), or in liquid form with a solvent. In those embodiments employing solvents, any solvent suitable for use in the formulation of a liquid detergent formulation may be employed. Suitable solvents include, for example, those solvents capable of dissolving anionic surfactants such as those described elsewhere herein. Examples of suitable solvents include, but are not limited to, water, alcohols, glycols and glycol ethers, cyclic carbonates, pine oil, methyl esters, limonene, aliphatic and aromatic hydrocarbons, or mixtures thereof. Specific examples of suitable alcohol solvents include, but are not limited to, alcohols having from about 1 to about 6 carbon atoms. In the practice of the disclosed method and compositions, typical specific solvents include water, straight chain alkyl alcohols containing from one to six carbon atoms (examples: methanol, ethanol, n-propanol, n-hexanol. etc.), branched chain alkyl alcohols containing from three to six carbon atoms (examples: isopropanol and secondary butanol), glycols such as propylene glycol, diglycols such as propylene diglycol and triglycols such as triethylene glycol and glycol ethers such as butylene glycol diethylether and dipropylene glycol methylether.

As described above, embodiments of the disclosed surfactant compositions include anionic surfactants/s blended or combined with one or more multi-functional polyetheramines. However, a wide variety of other optional ingredients may also be added if so desired. For example, one or more nonionic surfactants may also be added, for example, to lower mixture viscosity without destroying the salt, and/or in an amount sufficient to dissolve the anionic-polyetheramine, although greater or lesser amounts are also possible. In this regard, any nonionic surfactant or mixture thereof suitable for lowering the pour point may be employed.

Examples of suitable nonionic surfactants include, but are not limited to, nonylphenol ethoxylates, alcohol ethoxylates, ethylene oxide/propylene oxide ("EO-PO") block copolymers, alcohol ethylene oxide/propylene oxide adducts, and mixtures thereof. Specific examples include, but are not limited to, nonylphenol ethoxylates such as "SURFONIC® N- 95 available from Huntsman and linear alcohol ethoxylates such as "SURFONIC® L-24-7" also available from Huntsman. Other examples include, but are not limited to, nonionic surfactants commercially available from Huntsman Corporation and Witco, as described below.

Specific examples of suitable nonionic surfactants available from Huntsman Corporation include, but are not limited to, surfactants listed in Table 4.

Table 4

Specific examples of suitable nonionic surfactants available from Witco include but are not limited to, surfactants listed in Table 5.

Table 5

Specific examples of suitable nonionic surfactants available from Stepan include, but are not limited to, surfactants listed in Table 6.

Table 6

If desired, neutralization of anionic surfactants in the disclosed surfactant compositions may be accomplished with the addition of a basic compound. Examples of such optional neutralizing compounds include, but are not limited to, alkanolamines, alkyl amines, NFL-.OH, NaOH, KOH, and mixtures thereof. Amounts of neutralizing compound may be any amount suitable for partially or completely neutralizing an anionic surfactant acid. In one embodiment, an amount of neutralizing compound sufficient to neutralize about 75% of the anionic surfactant is employed, although greater or lesser amounts are also possible. Sufficient polyetheramine may be employed in conjunction with the neutralization compound to neutralize about 25% of the anionic surfactant.

Other additives may be employed, including materials know to those of skill in the art in the formulation of surfactant and/or detergent compositions. Examples include, but are not limited to, optical brighteners, anti-redeposition polymers, dye transfer inhibitors, preservatives, enzymes, builders, chelating agents, etc.

Compositions Adsorbed on Solid Carriers

In one embodiment, the disclosed multi-functional polyetheramine compositions may also be adsorbed onto solid carriers, alone or in combination with anionic and/or other surfactants. As used herein, a "solid carrier" is defined as any substantially free flowing solid material suitable for detergent or coating applications. Examples of types of suitable solid carriers include, but are not limited to, magnesium silicate particles, soda, ash, salt, clay, pigments, etc., mixtures thereof, etc. Examples of types and uses of such solid carriers with surfactants and defoamers may be found in United States Patent Application Serial No. 09/303,096 filed April 29, 1999, and entitled "Adsorbed Surfactants and Uses Therefor", which is incoφorated herein by reference.

In one example, multi-functional polyetheramine defoaming or anti-foaming compounds may be adsorbed, alone or in combination with surfactants, onto amorphous precipitated metallic silicate materials described elsewhere herein. In one exemplary embodiment, such amorphous magnesium silicate solid carrier materials may comprise compositions of the formula M_yO: X Si0₂, in which X is between 2.00 and 3.00 including every hundredth therebetween, and wherein M is a metal atom selected from the group consisting of a mono or divalent metal atom, and is most preferably an alkali metal or alkaline earth metal. In the case when M is a monovalent metal atom, the value of y may be 2. In the case when M is a divalent metal atom, the value of y may be 1.

Specific examples of such suitable magnesium silicate solid carrier materials include, but are not limited to, a family of compounds known as "MAGNESOL®" which are available from The Dallas Group of America, Inc. 1402 Fabricon Blvd., Jeffersonville, Indiana. These compounds are a synthetic amorphous hydrous form of magnesium silicate which are pure white, odorless, and tasteless having the approximate chemical formula MgO : 2.6SiO₂. The materials have a porous internal structure and a large activated surface area. Two such materials are known as "MAGNESOL® Super Flow" and "MAGNESOL® Flow Plus."

Advantageously, loadings of about 1:1 on a weight basis of polyetheramine anti-foaming agent (defoamer) to magnesium silicate are possible, while still producing a material which is free-flowing. Exemplary weight ratios of multi-functional polyetheramine to magnesium silicate include, but are not limited to, from about 1% to about 150%, alternatively from about 50% to about 100% by weight percent. However, greater and lesser weight percentage values are also possible.

When adsorbed surfactants are also present, multi-functional polyetheramine may be present in an amount of between about 1 weight % to about 75 weight % based on total weight of the composition, surfactant may be present in an amount of between about 1 weight % to about 75 weight % based on total weight of the composition, and magnesium silicate may be present in an amount of between about 25 weight % to about 99 weight % based on total weight of the composition. Alternatively multi-functional polyetheramine may be present in an amount of between about 1 weight % to about 50 weight % based on total weight of the composition, surfactant may be present in an amount of between about 1 weight % to about 50 weight % based on total weight of the composition, and magnesium silicate may be present in an amount of between about 50 weight % to about 99 weight % based on total weight of the composition. However, it will be understood that these weight percentages are exemplary only, and that the weight percentage of any given component may be greater or lesser than the values given in the ranges above.

Since magnesium silicate is useful as an anti-caking agent and possesses whiteness-improving characteristics when used in laundry detergents, precipitated magnesium silicate particles having an adsorbed polyetheramine antifoaming agent are capable of simultaneously functioning as an anti-foaming agent, anti-caking additive, and/or as a whitening agent, thus making preparation and use of detergents containing such materials more convenient and economical in comparison to conventional methods known in the art. In addition, consistency of manufactured quality from batch to batch of detergent using such materials may be greatly increased.

Production of solid carrier materials having surfactants and/or multi-functional polyethermines adsorbed thereon may be carried out in any manner of contacting or combining of solid carrier material with selected surfactants and/or polyetheramines suitable to achieve adsorption of one or more of these compounds onto the solid carrier. For example, one method my be carried out by first providing the material to be adsorbed (e.g., surfactant and/or polyetheramine), and by next causing the solid carrier (e.g., MAGNESOL®) to come into contact with the material to be adsorbed for a time period sufficient for adsorption. One exemplary method is given in Example 3.

In the practice of the disclosed methods and compositions, solid carrier materials having adsorbed multi-functional polyetheramines may be employed as anti-foaming agents or defoamers by combining them in aqueous solution with one or more surfactants, such as one or more of the anionic surfactants described herein. Alternatively, both multi-functional polyetheramine and anionic surfactant components may be adsorbed onto a solid carrier material that may be combined with an aqueous solution to form a liquid surfactant solution. A variety of other combinations are also possible, including solid carrier materials having adsorbed multi-functional polyetheramine and surfactant components (i.e., anionic, nonionic, and/or canonic surfactants), which may then be combined in solution with other surfactant/s of any given type.

Examples of uses for the disclosed multi-functional polyetheramine defoaming agents (incoφorated in either solid or liquid form) include, but are not limited to, wet or dry formulations for agricultural use (including, but not limited to, those employed as soil penetrants, defoliants, and herbicides); cement formulations for construction use; wet or dry coatings materials (including, but not limited to, paints and dry powder coatings formulations); in ink formulations for the printing industry; in asphalt emulsions used in the paving industry, sewage treatment facilities, etc.

EXAMPLES

The following examples are illustrative and should not be construed as limiting the scope of the invention or claims thereof.

In each of the examples 1 and 2, individual samples of surfactant solutions were evaluated for foaming characteristics using the following procedure:

100 grams of the test solution is charged to a Waring Blender and mixed at the low speed setting for 10 seconds. The contents of the blender are transferred immediately to a 1000 ml graduate cylinder and the foam height determined on the scale.

Example 1 - Foam Height as a Function of Concentration

A 2.5% by weight active solution of Cι₂-ι₄ 3EO ether sulfate (Sulframin SLES) was prepared in DI water with progressively increasing concentration of Jeffamine® D-2000. Each solution was charged to a Waring blender and mixed at low speed for 10 seconds. The results are shown in FIG. 1. With no added D-2000, the ether sulfate solution produced approximately 500 ml of foam. Addition of D-2000 dramatically decreased the amount of foam. This example shows that even small levels of polyetheramine is effective to suppress foam, and that amounts of about 2% or above are particularly effective. Example 2 - Polyetheramine Defoamer Evaluation Procedure

An evaluation study was performed to identify defoaming characteristics of various Jeffamine® products. In this work, 4% by weight of various Jeffamine® amines were added to samples of the 2.5% ether sulfate solution of Example 1. A control solution was formulated with a sample of the 2.5% ether sulfate solution of Example 1, but containing no amine additive. Other compounds tested in this and other examples herein are identified in Table 7 below.

Table 7

The foam heights were measured using the same procedure as in Example 1.

The Waring blender foam heights are given in FIG. 2. Among the effective products tested in this example were Jeffamine® products D-2000, D-4000, and T-5000. The results of this example indicate that in one embodiment, favorable defoaming characteristics may be achieved with a molecule that is multifunctional, relatively high molecular weight and based predominantly on propylene oxide.

Example 3 - Solid Defoamer Composition

Into a four-liter beaker half filled with selected liquid surfactant/s and/or multifunctional polyethermine/s is poured 100 grams of Flow Plus MAGNESOL®. The beaker is heated to 50 degrees Centigrade for 20 minutes, after which time the excess surfactant is filtered off using filtration methods well known to those of ordinary skill in the art. Alternatively, surfactant and/or polyetheramine may be mixed with water and sprayed onto a solid carrier and the water allowed or forced to evaporate.

Example 4 — Ethoxylated Jeffamine D-2000

Jeffamine D-2000 was modified by adding 4 moles of ethylene oxide to make the di- tertiary amine. Waring blend foam heights for sodium linear alkyl benzene sulfonate ("NaLAS", and in this case Huntsman "ALKYLATE 225™") are given in FIG. 3 as a function of unmodified Jeffamine D-2000 and modified concentration. The foam height decreases with increasing concentration of Jeffamine and levels off above 2%. Similar behavior is observed for both Jeffamine D-2000 and the modified (ethoxylated) version.

Example 5 - Additional Polyetheramine Defoamer Evaluation At Varying Concentration

Using methodology similar to Example 1, a 0.5% by weight active solution of sodium linear alkyl benzene sulfonate ("NaLAS", and in this case Huntsman "ALKYLATE 225™") was prepared in DI water with progressively increasing concentration of various amine compounds. 200 ml of each solution was charged to a Waring blender and mixed at low speed for 10 seconds. The results are shown in Table 8 below. With no added amine compound, the control 0.5% NaLAS solution produced approximately 1000 ml of foam. For the amine compound-containing solutions, 4% by weight of various identified amines were added to samples of the 0.5% NaLAS solution. The results of this example show that ethoxylated versions of the JEFFAMINE amines are also effective at defoaming aqueous solutions containing anionic surfactants.

Table 8

It will be understood with benefit of this disclosure by those of skill in the art that multifunctional polyetheramines disclose herein and having one or more primary amine groups may be alkoxylated using methods know in the art. For example, in one exemplary 0 embodiment a di-amine having two primary amine groups (such as Jeffamine D-2000) may be alkoxylated with 4 moles of alkylene oxide (such as ethylene oxide) by first combining the di-amine with four moles of alkylene oxide in the absence of catalyst to form a di-tertary amine. Further alkoxylation may be achieved with the use of a catalyst such as NaOH or KOH. While the invention may be adaptable to various modifications and alternative forms, specific embodiments have been shown by way of example and described herein. However, it should be understood that the invention is not intended to be limited to the particular forms disclosed. Rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims. Moreover, the different aspects of the disclosed compositions and methods may be utilized in various combinations and/or independently. Thus the invention is not limited to only those combinations shown herein, but rather may include other combinations.

REFERENCES

The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference.

U.S. Patent No. 3,776,962 U.S. Patent No. 5,152,933 U.S. Patent No. 5,167,872 U.S. Patent No. 5,719,118

U.S. Patent Application Serial Number 08/598,692. U.S. Patent Application Serial Number 09/141,660. U.S. Patent Application Serial Number 09/143,177. Cohen, L. et al., "Influence of 2-Phenyl Alkane and Tetralin Content on Solubility and

Viscosity of Linear Alkylbenzene Sulfonate," JAOCS, 72(1):115-122, 1995. Cox, Michael F. and Dewey L. Smith, "Effect of LAB composition on LAS Performance," INFORM, 8( 1 ): 19-24, January 1997.

Drazd, Joseph C. and Wilma Gorman, "Formulating Characteristics of High and Low 2-Phenyl Linear Alkylbenzene Sulfonates in Liquid Detergents," JAOCS, 65(3):398- 404, March 1988. Drazd, Joseph C, "An Introduction to Light Duty (Dishwashing) Liquids Part I. Raw Materials," Chemical Times & Trends, 29-58, January 1985.

Matheson, K. Lee and Ted P. Matson, "Effect of Carbon Chain and Phenyl Isomer Distribution on Use Properties of Linear Alkylbenzene Sulfonate: A Comparison of 'High' and 'Low' 2-Phenyl LAS Homologs," JAOCS, 60(9): 1693-1698, September 1983. Moreno, A. et al., "Influence of Structure and Counterions on Physicochemical Properties of Linear Alkylbenzene Sulfonates," JAOCS, 67(8):547-552, August 1990. Smith, Dewey L., "Impact of Composition on the Performance of Sodium Linear Alkylbenzenesulfonate (NaLAS)," JAOCS, 74(7):837-845, 1997; van Os, N. M. et al, "Alkylarenesulphonates: The Effect of Chemical Structure on Physico-chemical Properties," Tenside Surf. Det., 29(3):175-189, 1992.

Sweeney, W. A. and A. C. Olson, "Performance of Straight-Chain Alkylbenzene Sulfonates (LAS) in Heavy-Duty Detergents," JAOCS, 41 :815-822, December 1964.

Claims

WHAT IS CLAIMED IS:

1. A composition, comprising:

at least one anionic surfactant; and

at least one multifunctional polyetheramine comprising at least two amine groups per molecule, and having a molecular weight of at least about 1000;

wherein each of said amine groups is a secondary amine group, or a tertiary amine group; and

wherein none of the substituent groups attached to a nitrogen atom of said multifunctional polyetheramine is an n-propyl group or radical, or an alkyl group or radical having more than four carbon atoms.

2. The composition of claim 1, wherein said multifunctional polyetheramine has a molecular weight of from about 1000 to about 10,000 and comprises a di-functional amine, tri-functional amine, or a mixture thereof.

3. The composition of claim 2, wherein each tertiary amine group present comprises a nitrogen atom bound to three adjacent substituent groups, each of said adjacent substituent groups being (CH₂CH₂O)-H or (CH₂CH(CH₃)0)-H.

4. The composition of claim 3, wherein each of said amine groups is a secondary amine group or a tertiary amine group.

5. The composition of claim 2, wherein said polyetheramine and said anionic surfactant are adsorbed onto the surface of particles of hydrous metallic silicate, soda ash, salt, clay, pigments, or a mixture thereof.

6. The composition of claim 2, comprising from about 0.1 % to about 10% by weight multifunctional polyetheramine and from about 1% to about 30% by weight anionic surfactant; and further comprising water.

7. The composition of claim 2, wherein said multifunctional polyetheramine has a molecular weight of from about 2000 to about 5000.

8. A liquid surfactant composition, comprising:

at least one anionic surfactant;

at least one multifunctional polyetheramine, said multifunctional polyetheramine comprising two or three amine groups per molecule, and having a molecular weight of from about 1000 to about 10,000; and

solvent;

wherein said multifunctional polyetheramine is present in said composition in an amount effective to suppress foam in said composition when said composition is combined with water; and

wherein said multifunctional polyetheramine comprises a di-functional amine of the formula:

in which: x is from about 25 to about 100;

Ri is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)0)_n3-H;

R₄ is one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)O)_n -H;

and each of nl, n2, n3, and n4 may be independently from about 1 to 20; or

in which: b is from about 5 to about 50, and a+c is from about 2 to about 20;

R, is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H; R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)„₃-H;

R₄ is one of H, (CH₂CH₂0)_n -H, or (CH₂CH(CH₃)0)_n4-H;

and each of nl, n2, n3 and n4 may be independently from about 1 to

20; or

wherein said multifunctional polyetheramine comprises a tri-functional amine of the formula:

where: x+y+z is from about 5 to about 100;

Ri is one of H, (CH₂CH₂O)_nι-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ is one of H, (CH₂CH₂O)_π2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R₄ is one of H, (CH₂CH₂O)_n4-H, or (CH₂CH(CH₃)0)_n4-H;

R₅ is one of H, (CH₂CH₂0)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re is one of H, (CH₂CH₂O)_n6-H, or (CH₂CH(CH₃)O)_n6-H;

and each of nl, n2, n3, n4, n5 and n6 may be independently from about 1 to 20; or wherein said multifunctional polyetheramine comprises a tri-functional amine of the formula:

CH, CH,

R.

CH— O— (-CH— CH— θ )-(CH— CH — O-)— CH₂— CH — N

CH, CH,

^R3

CH— O— (-CH— CH— θ )-( CH— CH — O-)— CH₂— CH -N

R.

CH, CH,

,^R ₅

CH₂— O — (- CH — CH₂— O -)-(^• CH₂— CH — O -)— CH₂ CH — N

R,

in which: x+y+z equals from about 3 to about 100;

a+b+c equals from about 3 to about 30;

Ri is one of H, (CH₂CH₂O)„ι-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂O)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)0)_n3-H;

R4 is one of H, (CH₂CH₂O)_n -H, or (CH₂CH(CH₃)O)_n4-H;

R₅ is one of H, (CH₂CH₂O)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re is one of H, (CH₂CH₂O)_n6-H, or (CH₂CH(CH₃)0)_n6-H;

a mixture thereof.

9. The composition of claim 8, wherein said anionic surfactant comprises at least one of alkyl benzene sulfonate, alkyl sulfate, ether sulfate, secondary alkyl sulfate, α-olefin sulfonate, xylene sulfonate, alcohol sulfate, phosphate ester, napthalene sulfonate, sulfosuccinate, isethionate, carboxylate, betaine, soap, cyclic carbonates, pine oil, limonene, methyl esters, or a mixture thereof.

10. The composition of claim 8, wherein said multifunctional polyetheramine has a molecular weight of from about 2000 to about 5000.

11. The composition of claim 9, comprising from about 1% to about 5% by weight multifunctional polyetheramine; and from about 5% to about 15% by weight anionic surfactant.

12. The composition of claim 11, further comprising at least one nonionic surfactant.

13. The composition of claim 12, wherein said nonionic surfactant comprises at least one of alkylphenol ethoxylate, alcohol ethoxylate, ethylene oxide/propylene oxide block copolymer, alcohol EO/PO adduct, or a mixture thereof.

14. The composition of claim 8, wherein said solvent comprises water.

15. A composition comprising at least one multi-functional polyetheramine adsorbed onto the surface of particles of solid carrier; said multi-functional polyetheramine having a molecular weight of at least about 1000.

16. The composition of claim 15, wherein said multifunctional polyetheramine has a molecular weight of from about 1000 to about 10,000.

17. The composition of claim 16, wherein said solid carrier particles comprise at least one of magnesium silicate, sodium carbonate, salt, clay, pigment, or mixtures thereof.

18. The composition of claim 16, wherein said solid carrier particles comprise hydrous metallic silicate material of the formula M_yO : X Si0₂, wherein M is a metal atom, wherein X has a value of from about 2.00 to about 3.00; and wherein y has a value of 1 or 2.

19. The composition of claim 18, wherein said multifunctional polyetheramine comprises a di-functional amine of the formula:

in which: x is from about 25 to about 100;

Ri is one of H, (CH₂CH₂O)„ι-H, or (CH₂CH(CH₃)O)„ι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R_A is one of H, (CH₂CH₂0)_n -H, or (CH₂CH(CH₃)O)„₄-H;

and each of nl, n2, n3 and n4 may be independently from about 1 to 20; or

in which: b is from about 5 to about 50, and a+c is from about 2 to about 20;

R_! is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R_A is one of H, (CH₂CH₂O)_n4-H, or (CH₂CH(CH₃)O)_n -H;

and each of nl, n2, n3 and n4 may be independently from about 1 to 20; or

where: x+y+z is from about 5 to about 100;

Ri is one of H, (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂0)„₂-H, or (CH₂CH(CH₃)O)_n2-H; R₃ is one of H, (CH₂CH₂O)_n3-H, or (CH₂CH(CH₃)O)„₃-H;

R₄ is one of H, (CH₂CH₂O)_n -H, or (CH₂CH(CH₃)O)_n4-H;

R₅ is one of H, (CH₂CH₂O)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re is one of H, (CH₂CH₂O)_n6-H, or (CH₂CH(CH₃)O)_n6-H;

in which: x+y+z equals from about 3 to about 100;

a+b+c equals from about 3 to about 30;

Ri is one of H, (CH₂CH₂O)_nι-H, or (CH₂CH(CH₃)0)_n H;

R₂ is one of H, (CH₂CH₂O)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of H, (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R₄ is one of H, (CH₂CH₂O)_n4-H, or (CH₂CH(CH₃)O)_n4-H; R₅ is one of H, (CH₂CH₂O)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re is one of H, (CH₂CH₂O)„₆-H, or (CH₂CH(CH₃)0)_n6-H;

a mixture thereof.

20. The composition of claim 16, further comprising at least one anionic surfactant adsorbed onto the surface of said solid carrier particles.

21. The composition of claim 16, wherein said multifunctional polyetheramine is present in said composition in an amount of from about 1% to about 170% by weight based on total weight of said composition.

22. The composition of claim 18, wherein said hydrous metallic silicate particles have an average particle size of from about 1 micron to about 250 microns.

23. A method of suppressing foam in an aqueous surfactant system, comprising:

combining a multi-functional polyetheramine with said aqueous surfactant solution;

wherein said aqueous surfactant system comprises at least one anionic surfactant;

wherein said multi-functional polyetheramine comprises at least two amine groups per molecule, and has a molecular weight of at least about

1000; wherein each of said amine groups is a primary amine group, a secondary amine group, or a tertiary amine group;

wherein each tertiary amine group present comprises a nitrogen atom bound to three adjacent substituent groups, each of said adjacent substituent groups being (CH₂CH₂0)-H or (CH₂CH(CH₃)O)-H; and

wherein said multi-functional polyetheramine is present in an amount to suppress foam in said surfactant solution when said solution is combined with water.

24. The composition of claim 23, wherein each of said amine groups is a secondary amine group or a tertiary amine group; has a molecular weight of from about 1000 to about 10,000; and wherein said multifunctional polyetheramine comprises a di-functional amine of the formula:

in which: x is from about 25 to about 100;

Ri is one of (CH₂CH₂O)„,-H, or (CH₂CH(CH₃)O)_nι-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R4 is one of H, (CH₂CH₂O)_n4-H, or (CH₂CH(CH₃)O)_n4-H;

and each of nl, n2, n3 and n4 may be independently from about 1 to

20; or

in which: b is from about 5 to about 50, and a+c is from about 2 to about 20;

Ri is one of (CH₂CH₂0)„ι-H, or (CH₂CH(CH₃)0)_n*-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)0)_n2-H;

R₃ is one of (CH₂CH₂O)„₃-H, or (CH₂CH(CH₃)0)_n3-H;

R_A is one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)0)_n -H;

and each of nl, n2, n3 and n4 may be independently from about 1 to

20; or

where: x+y+z is from about 5 to about 100;

Rj is one of (CH₂CH₂0)_nι-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂0)_n2-H, or (CH₂CH(CH₃)O)„₂-H;

R₃ is one of (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)0)_n3-H;

. R₄ is one of H, (CH₂CH₂0)_n -H, or (CH₂CH(CH₃)0)„₄-H;

R₅ is one of (CH₂CH₂0)_n5-H, or (CH₂CH(CH₃)0)_n5-H;

Re is one of H, (CH₂CH₂0)_n6-H, or (CH₂CH(CH₃)0)_n6-H;

wherein said multifunctional polyetheramine comprises a tri-functional amine of the formula: CH, CH,

^Rι

CH— O— (-CH— CH₂— θ )-(CH— CH — O -)— CH₂— CH — N

A

CH, CH,

R,

CH— O — (- CH₂— CH₂- θ )-( cH— CH — O-)— CH₂— CH — N

R.

CH, CH,

R₌

CH— O— (-CH— CH₂— θ )-( CH₂— CH — θ )-CH₂ ^~-CH — N

R,

in which: x+y+z equals from about 3 to about 100;

a+b+c equals from about 3 to about 30;

Ri is one of (CH₂CH₂0)„i-H, or (CH₂CH(CH₃)0)_ni-H;

R₂ is one of H, (CH₂CH₂O)_n2-H, or (CH₂CH(CH₃)O)_n2-H;

R₃ is one of (CH₂CH₂0)_n3-H, or (CH₂CH(CH₃)O)_n3-H;

R₄ is one of H, (CH₂CH₂0)_n4-H, or (CH₂CH(CH₃)O)_n4-H;

R₅ is one of (CH₂CH₂0)_n5-H, or (CH₂CH(CH₃)O)_n5-H;

Re is one of H, (CH₂CH₂0)_ne-H, or (CH₂CH(CH₃)0)_n6-H;

a mixture thereof.

25. The method of claim 24, wherein said anionic surfactant comprises at least one of alkyl benzene sulfonate, alkyl sulfate, ether sulfate, secondary alkyl sulfate, α-olefin sulfonate, xylene sulfonate, alcohol sulfate, phosphate ester, napthalene sulfonate, sulfosuccinate, isethionate, carboxylate, betaine, soap, or a mixture thereof.

26. The method of claim 23, wherein said multifunctional polyetheramine is adsorbed onto a solid carrier.

27. The method of claim 25, wherein said multi-functional polyetheramine and said aqueous surfactant solution are combined in amounts effective to result in a solution comprising said anionic surfactant in an amount of from about 1% to about 30% by weight based on total weight of said solution, and said multi-functional polyetheramine in an amount of from about 1% to about 10% by weight based on total weight of said solution.