WO1999057203A1

WO1999057203A1 - Adsorbed surfactants and uses therefor

Info

Publication number: WO1999057203A1
Application number: PCT/US1999/009201
Authority: WO
Inventors: Ronald G. Lewis; George A. Smith; Samir S. Ashrawi
Original assignee: Huntsman Petrochemical Corporation
Priority date: 1998-05-01
Filing date: 1999-04-28
Publication date: 1999-11-11
Also published as: AU4069799A; BR9910331A; CA2329771A1; EP1075501A1

Abstract

Disclosed herein are compositions of matter comprising particles of amorphous metallic silicate species having a wide range of surfactants adsorbed thereon. The compositions comprise, in a preferred form of the invention, particles of amorphous alkaline earth silicates having alkoxylated surfactants adsorbed thereon, which particles are useful in a myriad of applications including without limitation ink formulations, toner compositions, agricultural formulations, and laundry detergent formulations.

Description

ADSORBED SURFACTANTS AND USES THEREFOR

CROSS REFERENCES TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application number 60/083,895 filed May 1, 1998.

TECHNICAL FIELD

This invention relates generally to a product comprising surfactants adsorbed onto a solid carrier. It relates more particularly to particular surfactants adsorbed onto magnesium silicate materials which possess high pore volumes, and to uses for the magnesium silicate/surfactant combination.

BACKGROUND INFORMATION

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. Surfactants are well 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 hydophillic portion within the same given surfactant molecule. When surfactants are in a solution, they 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, well-known property of surfactants is that they facilitate the wetting of solid surfaces by solutions. Since the presence of both hydrophobic and hydophillic 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 of these, the number of products available in the marketplace which fall under the classification of surfactant is very large,

indeed.

A wide variety of surfactants, including nonionic surfactants are available from Huntsman Petrochemical Corporation of 7114 North Lamar Blvd., Austin, Texas, including, but not limited to: SURFONIC® L24-4 (alcohol ethoxylate); SURFONIC® L24-9 (alcohol ethoxylate); SURFONIC® OP- 100; (alkylphenol ethoxylate) SURFONIC® JL80-X (alcohol alkoxylates); SURFONIC® N-120 (alkylphenol ethoxylate) ; and SURFONIC® TDA-8 (alcohol ethoxylate). Other surfactants commercially available as of this writing from Huntsman Petrochemical Corporation are in the public domain by virtue, inter alia, of several filings with various governmental Agencies. This includes a listing thereof, which also embraces the composition of the materials. The alkoxylation of alcohols and of alkylated phenols is well known in the chemical arts, and processes relating thereto are detailed in U.S. Patent Nos 4,760,200 and 5,256,828, the entire contents of each of which are herein incorporated by reference thereto.

U.S. Patent 5,631,205 to Killick et al., the entire contents of which are herein incorporated by reference, teaches the use of an adjuvant composition for use with a herbicide. U.S. Patent 5,550,115 to Garst et al., the entire contents of which are herein incorporated by reference, sets forth a dry composition useful as an adjuvant in the agricultural field. Typically, surfactants are employed in the agricultural art in order to increase the amount of biologically-active ingredient which is effectively delivered to the target species or area. Although the inventors hereof do not wish to be bound by any one particular theory, one mechanism for this is believed to be due to the ability of the surfactant material to increase the wettability of the surface of leaves on plants, or the surface of soil in order to promote increased absorption of the active chemical ingredient into the soil. By increasing the amount of active chemical which contacts leaves or penetrates soil makes the overall formulations more effective as a whole.

A family of compounds known as MAGNESOL® 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.

INVENTION SUMMARY

It has been discovered that when the aforesaid surfactant materials are adsorbed onto the above-mentioned hydrous amorphous magnesium silicate materials that the combinations obtained exhibit physical properties not possessed by either of the magnesium silicate or surfactant alone, which properties are wholly unexpected by the mere combination of the surfactant and particles of hydrous magnesium silicate. The silicate-based compositions according to the invention are of the formula M_yO : X SiO₂ having adsorbed onto the surface of the particles at least one surfactant, and 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 is preferably 2. In the case when M is a divalent metal atom, the value of y is preferably 1. DETAILED DESCRIPTION

Production of MAGNESOL® having surfactants adsorbed thereon may be carried out by first providing the surfactant to be adsorbed and next causing the MAGNESOL® to come into contact with the surfactant for a time period sufficient for adsorption. As an example, into a four-liter beaker half filled with one of the aforesaid liquid surfactants 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, the surfactant may be mixed with water and sprayed onto the MAGNESOL® and the water allowed or forced to evaporate.

Properties which are highly desirable in laundry detergent formulations are those known as whiteness retention and anti-redeposition. Table I below sets forth physical test results of laundry cleaned using the surfactants listed therein adsorbed onto the MAGNESOL® materials:

Surfactant MAGNESOL® OTHER MAT'L Negative Score

SURFONIC®L24-9 None 0.382

SURFONIC®L24-9 Flow Plus 0.160

SURFONIC®L24-9 Soda Ash 0.198

SURFONTC®JL80-X 0.687

SURFONIC®JL80-X Flow Plus 0.326

SURFONIC®JL80-X Soda Ash 0.945

TIDE® Ultra 0.368

PUREX® Ultra 0.761

Table I. In Table I., a lower negative (closer to zero) score indicates better performance. Thus, the best performance and hence most preferred embodiment of this invention with respect to whiteness retention and anti-redeposition is observed when Huntsman SURFONIC® L24-9 is adsorbed onto the Flow Plus MAGNESOL®. Employment of soda ash as a builder in laundry detergent formulations along with various surfactants is well-known. However, as the above examples show, the Huntsman SURFONIC® materials when adsorbed onto MAGNESOL® materials provide superior properties in the finished formulation respecting whitening power over soda ash.

The conditions of the testing for which the results in Table I. are reported were carried out on detergent test swatches obtained from Scientific Services S/D of Sparrowbush, NY. The test swatches selected for evaluation were: cotton 400 soiled with clay; cotton 400 soiled with dust sebum; 7535 WRL cotton/polyester permanent press soiled with clay; and 7535 WRL cotton/polyester permanent press soiled with dust sebum along with clean white swatches of each cloth type. The size of each swatch employed was 4 inches by 3 inches, and each had been dried in a 75 degree C oven for at least a 90 minute period prior to the evaluations.

The detergency evaluations were carried out using a Model 72436 Terg-O-Tometer ™, well-known to those skilled in detergent evaluation art employing one-liter wash/rinse solutions. The test conditions were: 95 degrees F., water hardness of 150 ppm as calcium carbonate, a Ca/Mg ratio of 2/1 and agitator revolution of 100-110 r.p.m.. Each Terg-O- Tometer™ pot contained three swatches of each soil/cloth type and two clean/white swatches of cloth type per test run. Each test run consisted of a ten minute wash followed by a five minute rinse. The rinse used deionized water at the test temperature. A complete test run consisted of three replicate runs, with random pot/test sample assignments for each run.

Data analysis was conducted with the aid of Minitab™ software. Actual analyses were conducted in the ANOV A/one-way analysis mode. The results of such analyses may be used for performance comparisons within that one test. However, when comparisons are made across different tests, these results are expressed as a percent of the Purex® standard detergent results. The results were recorded by a Hunter Lab COLORQUEST colorimeter. The comparison of each soiled swatch reading with its corresponding washed and dried swatch reading was recorded as its delta R (sub) x value. The use concentration for each experimental detergent (surfactant only, or surfactant/adsorbent combination) was adjusted, as close as possible so that 1.6 grams of surfactant was present in each wash liquor. The JLX-80 materials were evaluated at 25 % lower concentration than the rest of the experimental detergents. The standard detergents, Tide® Ultra liquid and Purex®Ultra liquid, were evaluated at a 1.6 gram/Liter level of the total formulated detergent.

Another use in which the aforementioned and other surfactants adsorbed onto amorphous metallic silicate materials, such as the MAGNESOL® materials, find particular advantage is as a carrier for anti-foaming agents. For example, it is a fact that traditional vertical-axis clothing washing machines in North America are being slowly 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 surfactants useful in controlling foaming. In

conventional powder detergents, foam control is typically achieved by adding a defoamer or anti-foaming agent to the formulation. The defoamer is typically present as a coating on particles of soda ash (sodium carbonate) at a level of between about 5 % to 10 %. Such materials are free flowing powders, which may be dry blended into various detergent formulations. An improvement to this approach is to use a precipitated metallic silicate, such as a magnesium silicate, including without limitation one of the MAGNESOL® materials aforementioned, as a carrier for the defoamer or anti-foam agent. Through use of the discovery of the instant invention, it has been found possible to achieve loadings of 1 : 1 on a weight basis of anti-foam agent (defoamer) to magnesium silicate, while still producing a material which is free-flowing ! Since magnesium silicate is known to be useful as an anti- caking agent and is known to possess whiteness-improving characteristics when used in laundry detergents, precipitated magnesium silicate particles having an adsorbed antifoaming agent are capable of functioning as an anti-foam, as an anti-caking additive, and as a whitening agent, thus making preparation and use of detergents containing such materials more convenient and economical with respect to the methods known in the art. In addition, consistency of manufactured quality from batch to batch of detergent using such materials shall be greatly increased.

In order to exemplify the foregoing, without limitation, a series of low foam surfactants were adsorbed on the magnesium silicate known as MAGNESOL® 3040, (available from Dallas Group of America, Jeffersonville, Indiana 47130), Each surfactant in the test series being present at a 1:1 loading by weight (anti-foam : Mg Silicate), by simple admixture ^"of the magnesium silicate with the surfactant to form a magnesium silicate / surfactant adduct product ("Adduct"). In the case of each of the

surfactants tested, a free-flowing powder resulted from such 1 :1 (by wt.) admixture. For each anti-foam agent adsorbed on the magnesium silicate, a test was run to determine the usefulness of the adsorbed surfactant / silicate combination with respect to breaking a foam. The testing was performed on solutions prepared from mixing a powdered laundry detergent composition (which powdered composition included the Adduct material formed from each surfactant tested), and subjecting the solution to conditions under which a heavy foam would be produced. The foam produced in each case was observed and comparisons were made. For each of the tests, the powdered stock was mixed with and dissolved in distilled water at a level of 1.25 grams of the powdered stock per liter to provide a solution to be tested. The powdered stock itself consisted in each case of 4.0 % by weight of the magnesium silicate / surfactant Adduct under evaluation, and 96.0 % by weight of Tide Ultra® powdered laundry detergent, which powdered stock was thoroughly mixed by tumbling. In each case, to a Waring® "Commercial Laboratory Blender" of 5 cup capacity, was added 200 grams of the solution to be tested. The blender was energized on its low speed setting for 30 seconds, after which time the blender was turned off and the contents of the blender immediately poured into a 900 milliliter graduated cylinder. After a five minute setting period during which time the solution was permitted to rest motionless on a tabletop at room temperature, the volume of foam present in the graduated cylinder was recorded. The results of the foam readings thus obtained are set forth below in Table I.

Sample ID Surfactant Foam Volume (ml)

1 No added Adduct 470 ml

2 TA-100 290

3 TEGO-3062 450

4 SE-26 440

5 S-204 300

6 S-133 330

7 Antifoam-A 390

8 Surfonic® LF-41 420

9 Surfonic® LF-27 460

10 Surfonic®LF-17 450

11 ASP-15 280

12 ASP-8 320

Table I - Foam volumes of agitated detergent solutions containing various antifoam agent / magnesium silicate Adducts at 50% antifoam agent loading.

In Table I, various abbreviations are given for anti-foaming agents employed therein. The abbreviations are actually tradenames under which the products are marketed by their producers. TA-100 is an antifoam agent available from Taylor Chemical Company Inc., of Lawrenceville, Georgia; TEGO 3062 is an antifoam agent available from Goldschmidt Chemical Corporation of Hopewell, Virginia; SE-26, S-204, S-133, ASP-8, and ASP-15 are antifoam agents available from Wacker Silicones Corporation of Adrian, Michigan; Antifoam- A is an antifoam agent available from Dow Chemical Company of Midland, Michigan; the Surfonic® LF-41, Surfonic® LF-27, and Surfonic® LF-17 are antifoam agents available from Huntsman Petrochemical Corporation of Austin, Texas. The instance in the example of Table I where TA-100 is employed is the most preferred form of the invention for reducing foam in laundry applications.

Sample 1 in Table I above contained no Adduct, and is therefore useful as a reference standard by which the performance of the other solutions may be gauged. As can be seen from these data, significant decreases in foam volume are obtainable when certain Adducts are employed, in which the Adducts are formed from mixing an anti-foam agent and a surfactant in a ratio of 1:1, in accordance with the most preferred form of the invention, other ratios of surfactant to magnesium silicate are now indicated as providing useful compositions of matter in accordance with the invention, including ratios in the range of 0.01 : 1 to 1.70 : 1 and every hundredth therebetween.

Another use anticipated for the aforementioned and other surfactants adsorbed onto MAGNESOL® materials is in wet or dry formulations for agricultural use including, but not limited to, those employed as soil penetrants, defoliants, and herbicides. The MAGNESOL®, which has the surfactant adsorbed thereon, is incorporated into a wet or dry formulation for the above uses. The surfactant may be either cationic, anionic, or preferably non-ionic.

Another use anticipated for the aforementioned and other surfactants adsorbed onto MAGNESOL® materials is in cement formulations for construction use. The MAGNESOL®, which has the surfactant adsorbed thereon, is incorporated into a wet or dry

10 formulation for cement. The surfactant may be either cationic, anionic, or preferably non-

ionic.

Another use anticipated for the aforementioned and other surfactants adsorbed onto MAGNESOL® materials is in wet or dry coatings materials including, but not limited to, paints and dry powder coatings formulations. The MAGNESOL®, which has the surfactant adsorbed thereon, is incorporated into a wet or dry formulation for the above uses. The surfactant may be either cationic, anionic, or preferably non-ionic.

Another use anticipated for the aforementioned and other surfactants adsorbed onto MAGNESOL® materials is in ink formulations for the printing industry. The MAGNESOL®, which has the surfactant adsorbed thereon, is incorporated into an ink formulation. The surfactant may be either cationic, anionic, or preferably non-ionic.

Another use anticipated for the aforementioned and other surfactants adsorbed onto MAGNESOL® materials is in asphalt emulsions used in the paving industry. The MAGNESOL®, which has the surfactant adsorbed thereon, is incorporated into the asphalt formulation. The surfactant may be either cationic, anionic, or preferably non-ionic.

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Claims

We claim:

1) A composition of matter comprising particles of hydrous metallic silicate of the formula M_yO : X SiO₂ having adsorbed onto the surface of the particles at least one surfactant, wherein M is a metal atom, and in which X is between 2.00 and 3.00 including every hundredth therebetween.

2) The composition as set forth in claim 1 wherein said hydrous metallic silicate particles have a particle size, as measured in microns, between 1 and 250, including every whole integer therebetween.

3) The composition according to claim 1 wherein y is 1 and M is a divalent metal atom.

4) The composition according to claim 3 wherein said metal M is selected from the group: calcium and magnesium.

5) The composition according to claim 1 wherein y is 2 and M is a monovalent metal atom.

6) The composition according to claim 5 wherein said metal M is selected from the group consisting of: sodium and potassium.

7) The composition of claim 1 wherein said surfactant is selected from the group consisting of: anionic surfactants, non-ionic surfactants, and cationic surfactants.

12 8) The composition of claim 1 wherein the amount of surfactant present in the composition is between 0.01 and 1.70, and every hundredth therebetween, by weight based upon the total weight of the composition.

9) The composition of claim 1 wherein said surfactant is an alkoxylated surfactant.

10) The composition of claim 9 wherein said alkoxylated surfactant is selected from the group consisting of: alkoxylated alcohols and alkoxylated alkyl phenols.

11) The composition of claim 10 wherein said alkoxylated surfactant is an alkoxylated alcohol derived from an alcohol containing between 3 and 20 carbon atoms per molecule, said alcohol being either straight-chain or branched, and saturated or unsaturated.

12) The composition of claim 10 wherein said alkoxylated surfactant is derived from an alkyl phenol which comprises phenol having at least one alkyl group attached to the aromatic ring in either the ortho, para, or meta positions.

13) The composition of claim 12 wherein said at least one alkyl group contains between 3 and 20 carbon atoms per molecule, wherein said at least one alkyl group is straight-chain or branched and is either saturated or unsaturated.

13 14) The composition according to claim 10 wherein said alkoxylated surfactant is prepared by alkoxylation process that employs at least one alkylene oxide selected from the group consisting of: ethylene oxide, propylene oxide, and butylene oxide.

15) The composition according to claim 14 wherein the number of moles of alkylene oxide incorporated into said surfactant is between 2 and 50, including every whole integer therebetween.

16) A laundry detergent composition comprising: sodium carbonate, and a particulate hydrous magnesium silicate having a surfactant adsorbed on the particles thereof, wherein said magnesium silicate is described in any of claims 1 - 14.

17) A composition of matter useful in agriculture which comprises: a surfactant adsorbed onto a particulate hydrous magnesium silicate of the formula MgO : X SiO₂ wherein X is between 2.00 and 3.00 including every hundredth therebetween, and at least one material selected from the group consisting of: herbicides, defoliants, insecticides, fungicides, and fertilizers.

18) The composition of claim 17 wherein said surfactant is selected from the group consisting of anionic surfactants, non-ionic surfactants, and cationic surfactants.

14 19) The composition of claim 18 wherein the amount of surfactant present in the composition is between 0.01 and 1.70, and every hundredth therebetween, by weight based upon the total weight of the surfactant.

20) The composition of claim 19 wherein said surfactant is an alkoxylated surfactant.

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