WO1996000253A1

WO1996000253A1 - A surface active composition containing an acetal or ketal adduct

Info

Publication number: WO1996000253A1
Application number: PCT/US1995/007886
Authority: WO
Inventors: Mark S. Felix
Original assignee: The Dow Chemical Company
Priority date: 1994-06-23
Filing date: 1995-06-21
Publication date: 1996-01-04
Also published as: AU2869595A

Abstract

Disclosed is a composition which comprises an acetal or ketal adduct of a monohydroxyl-terminated polyoxyalkylene. Such compositions find value as components in cleaning methods, methods of controlling foam formation, drilling muds, and in formulations for use as cosmetics, pharmaceutics and pesticides, where modification of surface active properties may be desired.

Description

A SURFACE ACTIVE COMPOSITION CONTAINING AN ACETAL OR KETAL ADDUCT

This invention relates to surfactants and more particularly to compositions which comprise a polyoxyalkylene acetal or ketal, and a process for preparing the same.

Products having surface active properties, commonly called surfactants or stabilizing agents, are widely used in many industrial, agricultural and pharmaceutical applications where it is necessary to modify hydrophobic/hydrophilic surface interactions. Frequently employed surfactants include liquid polyoxyalkylene polymers and silicon-based polyoxyalkylene polymers. However, in recent times there has been an increasing awareness of environmental and ecological aspects for many applications, especially where possibility of an accumulation of such surfactants in the environment exists to the potential detriment of established ecosystems. Accordingly, it would be desirable to use a surfactant product which possesses a greater activity and therefore could be deployed in smaller amounts to achieve the same technical result. Use of smaller amounts would lead to a significantly reduced environmental accumulation potential. Alternatively, it would be desirable to use a surfactant which can be more readily biodegraded. In the optimum, it would be desirable to use a surfactant which exhibits a greater activity in the application area and which further has an attractive degree of biodegradability. Certain substances are known from the art to have surfactant activities and additionally exhibit some biodegradability, such substances include ketals and acetals as discussed in the patent document EP-A-512,501. Thus, the preparation of alternative surfactants comprising acetal adducts has been investigated with a view to obtaining an enhanced surfactant activity and eventually enhanced biodegradability. The assessment of surface activity can be conveniently determined by observing the change of surface tension of water with concentration of the adduct. When, upon addition of the adduct, the surface tension of water ceases to change (normally decrease) the critical micelle concentration (CMC) forthe adduct has been attained. A lower CMC value is taken as indicating a greater surface activity.

In the art, it is known to prepare acetal or ketal products by reacting an alcohol with an aldehyde, or ketone, respectively, in the presence of an acid catalyst. Such procedures are disclosed in various patent documents including GB 1,178,988; EP-A-164,425; EP-A-525,626; DE 33 18592; DE 3441 542; U.S. 2,556,559; U.S. Patent 2,840,615; U.S. Patent 4,024,159; and U.S. Patent 4,579,979.

In the alternative, acetals or ketals may be obtained by reacting an alcohol with a vi nyl ether or olefi n. U.S. Patent 3,024,284 d iscl oses a process for the preparati on of si m pie ketals by reacting a lower secondary alcohol with an alpha-unsaturated ether in the presence of an acid catalyst. U.S. Patent 3,931 ,337 discloses the preparation of multiblock polyacetal copolymer surfactants by reacting a polyoxyalkylene polymer with a lower alkyl vinyl ether followed by thermal coupling of the acetal-terminated polymers to give the final product. U.S. Patent 3,954,886 discloses the preparation of polyoxyethylene acetal surfactants by the sequential reaction of polyoxyethylene diols with a high molecular weight alkyl vinyl ether followed by a low molecular weight alkyl vinyl ether. U.S. Patent 3,244,753 discloses the preparation of acetals of mono- and polyoxyalkylene glycols with vinyl ethers in the presence of an acid catalyst and specific phosphorus compounds to prevent the formation of colored products. U.S. Patent 2,905,719 discloses the preparation of acetal surfactants by reacting vinyl ethers containing from 8 to 18 carbon atoms with ethoxylated alcohols. German patent DE 22 52 186 discloses the preparation of a surfactant by reacting a polyoxyalkylene polyoi, predominantly oxypropylene, with an excess of an alkyl vinyl ether in the presence of an acid catalyst. Despite the seemingly extensive knowledge relating to acetal/ketal surfactants there is still a need to develop alternative products with a view to optimizing activity and/or biodegradability properties. In one aspect, the present invention is a composition comprising a hydroxyl-

-terminated polyoxyalkylene and an acetal or ketal characterized in that: a) the acetal or ketal, present in an amount of from 1 to 99 percent by weight based on total parts by weight of the composition, is an adduct of a monohydroxyl-terminated polyoxyalkylene; and b) the composition exhibits a critical micelle concentration (CMC) in water of less than 25 ppm of water at 25°C.

In another aspect, the present invention is a fatty alcohol alkoxylate composition which contains from 1 to 99 parts per 100 parts by total weight of the composition of an acetal mixture comprising components (a) and (b) wherein said mixture is characterized in that, based on the total parts by weight of (a) and (b) present, it comprises: a) from 1 to 99 weight percent of a substance corresponding to Formula (I), and

F - (AO)_n - O - CH - O - (AO)n - F

I (I)

CH₃ b) from 99 to 1 weight percent of a substance corresponding to Formula (II),

F - (AO)n - 0 - CH - O - R

I (ID;

CH₃ wherein F is independently a hydrocarbyl radical having from 6 to 30 carbon atoms; AO is independently a C₂-4 oxyalkylene moiety where more than 50 mole percent of the oxyalkylene moiety is a C₂ substance; n is independently a number of from 3 to 30; and R is a hydrocarbyl radical having from 1 to 5 carbon atoms.

In yet another aspect the present invention is a process for preparing a fatty alcohol alkoxylate, as mentioned above, characterized in that a monohydroxyl-terminated polyoxyalkylene or fatty alcohol alkoxylate is reacted, in the presence of an acid catalyst, with an alkyl vinyl ether present in an amount to provide from 0.05 to 0.98 equivalents per hydroxyl group.

In other aspects, this invention relates to the following methods and formulations of industrial relevance using one of the above-mentioned compositions, to modify any hydrophilic/hydrophobic or lipophilic/iipophobic interaction, including:

(i) A method for stabilizing oil or gas well walls which comprises using an invert- -emulsion or emulsion drilling mud wherein the invert-emulsion drilling mud contains from 0.5 to 100 percent by weight, and the emulsion drilling mud includes from 0.5 to 50 percent by weight, of one of the above-mentioned compositions.

(ii) A method for controlling foam formation of an aqueous or non aqueous mixture in an environment with free surface turbulence which comprises bringing said mixture into contact with from 0.0001 to 10 percent by weight of one of the above-mentioned compositions. Exemplary of situations where control of foam formation is desirable include the paper, pulp and food processing industries.

(iii) A method for cleaning which comprises bringing a surface to be cleaned into contact with a cleansing agent which includes one of the above-mentioned compositions. Particular examples of such a method are the industrial cleaning methods for dairy or brewery equipment. (iv) A method for dispersing oil spills on water which comprises treating an oil- contaminated water surface with a dispersing agent that includes one of the above-mentioned compositions.

(v) A method to mercerize textile threads, in particular cellulose-based threads such as for example cotton, by treatment with a caustic solution in the presence of one of the above-mentioned compositions.

(vi) A cleaning formulation, in particular a laundry detergent, which comprises a component being one of the above-mentioned compositions.

(vii) A cosmetic formulation which comprises one of the above-mentioned compositions. (viii) A pesticide formulation comprising an active component such as a herbicide, insecticide, fungicide, or bactericide, and a further component being one of the above- -mentioned compositions.

(ix) A pharmaceutical formulation containing a physiologically active component and a further component being one of the above-mentioned compositions. The attractive surface activity and biodegradability properties of the composition of this invention allows it to conveniently substitute for many of the nonionic surfactants, especially oxyalkylene adducts of fatty alcohols, presently used in industry. The composition of this invention comprising a hydroxyl-terminated polyoxyalkylene and an acetal or ketal adduct of a monohydroxyl-terminated polyoxyalkylene exhibits a critical micelle concentration (CMC) in water of less than 25, preferably less than 20, more preferably less than 15, and yet more preferably less than 10 ppm of water at 25°C. Such CMC performance can be obtained with a composition which, based on total parts by weight of the composition, comprises from 1 to 99 percent by weight of adduct, preferably an acetal adduct. Advantageously, the adduct is present in an amount of from 5, more preferably from 10, yet more preferably from 15, and yet still more preferably from 20 weight percent; and preferably up to 95, more preferably up to 90, yet more preferably up to 80, and yet still more preferably up to 60 weight percent. The balance of the composition is a hydroxyl-terminated polyoxyalkylene, and particularly a monohydroxyl-terminated polyoxyalkylene such as, for example, an oxyalkylene derivative of an aliphatic fatty alcohol, optionally unsaturated. The provision of a limited acetal/ketal content of the composition is desirable to provide for an enhanced biodegradability and, a reduction of potential aquatic toxicity. The acetal/ketal content also provides the composition with a better resistance to basic conditions rendering it especially suitable for applications where attractive stability under basic conditions is desirable.

In a preferred embodiment of this invention, the composition comprises an acetal mixture which, based on the total parts by weight of components (a) and (b) present, comprises: a) from 1 to 99 weight percent of a first acetal substance corresponding to

Formula (I),

F - (AO)_n - O - CH - O - (AO)n - F

I (I)

CH₃ and b) from 99 to 1 weight percent of a second acetal substance corresponding to

Formula (II),

F - (AO)n - O - CH - O - R

I (ID

CH₃ wherein, is independently a hydrocarbyl radical, optionally unsaturated, having from 6 to 30 carbon atoms;

AO is independently a C_2-4 oxyalkylene moiety, and preferably where more than 50 mole percent of the oxyalkylene moiety is a C₂ substance; n is independently a number of from 3 to 30; and R is a hydrocarbyl radical having from 1 to 5 carbon atoms. Further to the first and second acetal substance, the mixture may additionally contain a third acetal substance corresponding to Formula (III): R - O - CH - O - R

I (HI)

CH₃ with R being as stated for (I) or (II). The third acetal substance may be present in an amount of from 0.1 to 15 weight percent of the total acetal mixture comprising the first, second and third acetal substances.

The acetal mixture advantageously contains the first acetal substance preferably in an amount of from 5, more preferably from 20, and yet more preferably from 40; and preferably up to 95, more preferably up to 80 and yet more preferably up to 60 weight percent.

In compliment, the acetal mixture advantageously contains the second acetal substance 0 preferably in an amount of up to 95, more preferably up to 80 and yet more preferably up to

60; and preferably from 5, more preferably from 20, and yet more preferably from 40 weight percent.

To provide for the desired degree of biodegradability, the hydrocarbyl radical F advantageously is a linear group which preferably contains from 8, and preferably up to 25, -> more preferably up to 18, and yet more preferably up to 15 carbon atoms. Carbon-carbon unsaturation may also be present within the hydrocarbyl radical F.

To provide for the desired degree of surface activity, the hydrophobic/lipophiiic nature conferred by the presence of the hydrocarbyl radical F should be complimented by a hydrophilic/lipophobic moiety, in this case the oxyalkylene chain of limited length. For this 0 purpose, the value "n" preferably is from 5, more preferably from 7, and preferably up to 20, and more preferably up to 12.

In a highly preferred embodiment, the hydrocarbyl radical F contains from 8 to 12 carbon atoms, and the value "n" is from 7 to 12.

The hydrocarbyl radical R can be any (cyclo) alkane. For reasons of commercial ⁵ availability and convenience of handling liquid reactants, the hydrocarbyl radical R preferably comprises from 1 to 5 carbon atoms and advantageously is a * or C5 radical, including the n- or i-isomers of butyl or pentyl radicals.

The remaining part of the composition is a hydroxyl-terminated polyoxyalkylene which is a polyoi or, preferably, a monohydroxyl substance. When the hydroxyl-terminated ^υ polyoxyalkylene is a monohydroxyl substance, it is advantageously an oxyalkylene derivative of a fatty alcohol having the general formula:

F - (AO)_n - OH (IV) wherein F, AO, and n are as described above.

As mentioned, this invention also relates to a process for the preparation of the 5 above-described composition comprising a ketal, or preferably acetal, adduct by reacting a limited amount of an alkyl vinyl ether with a monohydroxyl-terminated polyoxyalkylene in the presence of an acid catalyst. The amount of alkyl vinyl ether present in the process is up to a stoichiometric equivalent per hydroxyl group of the monohydroxyl-terminated polyoxyalkylene. Advantageously, the amount of vinyl ether is from 0.05, preferably from 0.1, more preferably from 0.15, and yet more preferably from 0.2; and preferably up to 0.98, more preferably up to 0.95, yet more preferably up to 0.8, and still more preferably up to 0.75 equivalents per hydroxyl group of the polyoxyalkylene. It is presently understood that the alkyl vinyl ether reacts with the monohydroxyl-terminated polyoxyalkylene to provide an acetal corresponding to Formula (II) which, under the acidic process conditions and elevated temperature, subsequently undergoes transacetalization to provide acetal corresponding to Formula (I) and Formula (III). The ability for a transacetalization reaction to occur is enhanced bythe use of substoichiometric amounts of the vinyl ether and further, as will be shown, provides for some control over the formation of the different acetal substances as already described. It is to be noted that depending on the particular R group, acetal corresponding to Formula (III) may be volatile and susceptible to removal under the conditions employed to manufacture the composition. In this case, the end composition may not contain acetal (I) and acetal (III) type components in commensurate proportions.

Some control of the degree of formation of the first, second, and third acetal substances can be exercised by selection of reaction temperature and rates of addition of the vinyl etherto the monohydroxyl-terminated polyoxyalkylene. To promote the transacetalization reaction, the reaction temperature is, advantageously, at least 30°C, preferably from 30°C to 100°C, and more preferably from 40^CC to 80°C. At higher temperatures an undesirable color of the composition can result. It is found that under the acid catalyzed conditions and elevated temperature that reaction of the vinyl ether proceeds relatively quickly and that addition times ranging from a few minutes to 10 hours, and typically from 10 minutes to 2 hours provide for essentially complete conversion of the vinyl ether. It is observed that higher rates of addition of the vinyl ether generally favor the transacetalization reaction. Suitable monohydroxyl-terminated polyoxyalkylene substances for use in the process include an oxyalkylene adduct of a fatty alcohol having the formula:

F - (AO)_n - OH (IV) wherein F, AO, and n are as given above. The AO moiety advantageously comprises a majority of C₂, oxyethylene, units. The term "majority", means substances wherein more than 50, preferably at least 65, more preferably at least 80, and up to 100 mole percent of the total oxyalkylene content is oxyethylene. Preferably, the monohydroxyl-terminated polyoxyalkylene contains a hydrophobic substituent having from 6 to 30 carbon atoms. A wide variety of oxyalkylated fatty alcohols are generally commercially available and obtained bythe reaction of a fatty alcohol with an alkylene oxide including notably propylene oxide, butylene oxide and especially ethylene oxide, usually in the presence of an alkaline catalyst. Oxyalkylated fatty alcohols particularly well suited for use in the process of this invention are those which do not have any appreciable free salt content, as can be acquired by the in situ acid treatment of the alkali catalyst used in the manufacture of the oxyalkylated fatty alcohol. The presence of an appreciable amount of free salt can be detrimental to the formation of acetal and eventual effectiveness of the composition in the chosen application area. If free salt is present, it is, advantageously, less than 100 ppm, and preferably less than 50 ppm of oxyalkylated fatty alcohol.

Suitable alkyl vinyl ethers for use in the process correspond to those having the general formula:

R - O - CHY -= CH₂ (V) wherein R is as mentioned above; and Y, when intending to prepare an acetal adduct is hydrogen and, when intending to prepare a ketal can be any (cyclo) alkyl, aryl or heterocyclic radical but advantageously is a C C₆ alkyl or aryl radical.

As mentioned, the reaction takes place in the presence of an acid catalyst. Such acid catalyst can be a free acid, such as for example p-toluene sulphonic acid. Preferably, for avoidance of its subsequent removal, the acid catalyst is present on a fixed bed in which case an acidic ion-exchange resin can be employed to advantage.

Although it is preferred to obtain the acetal or ketal containing composition directly bythe above-mentioned process, it is envisaged that the final acetal/ketal content of the so obtained composition could be modified by subsequently adding a desired amount of a hydroxyl-terminated polyoxyalkylene free of any acetal/ketal substances. In a less preferred embodiment, it is also contemplated that the desired composition could be obtained by blending a pure acetal or ketal substance(s) with a hydroxyl-terminated polyoxyalkylene free of any acetal/ketal substance in the appropriate proportions.

The following examples are given to more fully illustrate the present invention. As such they are not intended to be, nor should they be construed as being, limitative of its scope in any way. All parts and percentages are based on weight unless otherwise indicated. Example 1

Acetal-containing compositions, Compositions 1 to 4, are prepared according to the following general procedure. Amounts of substances where not mentioned in the general procedure are identified in Table I. A reactor is charged with a given amount of an alkoxylated fatty alcohol (FAE) represented bythe formula CιoO-(C₂H₄0-) H, and 3.1 parts by weight of an acidic ion- -exchange resin DOWEX 50 W8 available from The Dow Chemical Company. The resulting mixture is brought to a temperature of 105°C at a reduced pressure of lO mbar and maintained under these conditions for approximately 2 hours to minimize any water content. The "dried" mixture is then broughtto 50°C and ambient pressure, under nitrogen, prior to introducing a given amount of isobutyl vinyl ether (IBVE). The IBVE is introduced in one portion with continuous agitation of the mixture. After 30 minutes, the resulting reaction product is filtered to remove acidic ion-exchange resin providing a pale yellow to colorless acetal-containing composition. Certain physical properties of the resulting acetals compositions are reported in Table I along with the relative concentrations of the acetals corresponding to Formulae I, II, and 111 as observed by ¹³C NMR (CD₃COCD₃). The physical properties are observed according to the following test procedures, for: wetting times DIN 53901 ; foam behavior according to the "Ross-Miles" test, ASTM-D-1173; and aqueous cloud point, ASTM D-2024.

The critical micelle concentration (CMC) is determined by measuring the surface tension of water at 25°C according to the Du Nuoy Ring Method in the presence of varying concentration (ppm) of the compositions. The variance of surface tension with concentration of the composition is plotted and the point at which the surface tension ceases to change (decrease) with increasing concentration is taken as being the CMC value. Example 2

Composition 5 is prepared according to the above general procedure with reactants in the proportions as indicated for Composition 2 except, in this instance, the total amount of IBVE is added in small increments over a period of 30 minutes and the resulting mixture stirred for a further 30 minutes prior to removing the ion-exchange resin.

Compositional analysis and physical properties of Composition 5 are also reported in Table I.

With reference to the data reported in Table I, the following comments are given. The pour point temperature of the composition increases with decreasing total acetal content of the composition. Better foam control is exhibited by compositions having a higher total acetal content. The cloud point temperature of the composition generally increases with decreasing total acetal content of the composition. However, unexpectedly the cloud point can be significantly influenced bythe distribution of the different acetal components. For example, Composition 5 has approximately the same total acetal content as that of Composition 2 and yet exhibits a significantly higher cloud point temperature. The ability to influence cloud point in such a manner enhances the value of the compositions for applications where susceptibility to unwanted, unattractive, turbidity may be encountered. Example 3

The biodegradability of substances is evaluated in an aerobic aqueous medium with the Manomeric Respirometry test according to published OECD Guidelines for testing of Chemicals Number 301 F and Method C.4-D in Commission Directive 92/69/EEC. Substances are considered as being readily biodegradable if the extent of biodegradation is more than 60 percent after 28 days.

Based on oxygen consumption after 28 days, Compositions 2 and 4 exhibited a biodegradability ranging from 72 to 81 percent. By way of comparison in the same evaluation, a representative commercially available oxyethylene-oxypropylene Cι₃-fatty alcohol having an oxyethylene:oxypropylene weight ratio of 85: 15 exhibits a biodegradability of 34 percent. Table I

wt% of FAE and Foam CMC in

IBVE total acetal Pour Cloud Wetting Behavior, water at

FAE pbw/ content in Relative wt% of Point Point Time "Ross-Miles" 25°C

Composition pbw mole eq. composition different acetals (°c) (°C) (sec) (mm) (ppm)

0 300

FAE Acetal I II III in min

1 124.3 27 / 1.0 4 96 41.7 51.2 7.0 - 12.4 2.5 42 2 0 7.5

19.4 /

2 130.7 21.6 78.4 48.8 46.2 4.9 - 10 13.5 0.7 48 15 0 6

I 3 12.9

137.4 40.1 59.9 57.6 39.4 3.0 - 3 /0.45 28 71 20 2 3 f

4 6.5 /

143.6 0.2 65 35 71.5 27.2 1.2 - 4 46 44 60 8 6

19.4 /

5 130.7 26.5 73.5 9.3 89 1.6 - 10 0.7 23.9 48 10 0 /

A* 100 / 100 / / / / 0 71 39 140 100 500

* Not an example of this invention

Example 4

The value of the compositions of this invention for cleaning applications, where additional control of foam formation can be important, is demonstrated by the following example where the compositions are used to substitute for a standard nonionic surfactant in a typical all-purpose cleaning formulation.

The performance of the cleaning formulation is observed according to the industrially accepted Industrieverband fuerPutz and Pflegemittel (IPP) test. A weighted sponge having absorbed on to it the cleaning solution is mechanically moved backwards and forwards (a total of 10 passes) over a soiled substrate, which has also been wetted with the o cleaning solution. The cleaned substrate is then washed in running water before it is measured for comparative cleanliness. The "soiling" of the substrate, a clear plastic strip to which a wrinkled, white, PVC strip has been attached, consists of carbon black and oleochemicals. The cleaning efficiency, of the formulation is determined by measuring the whiteness of the cleaned substrate via the reflectance of light and comparing it to that of the original surface. 5 The foam control potential of the formulation is demonstrated by a modified

Ross-Miles test in which 200 mL of tap water is dropped from a height of 1 meter on to 3.2 mL of the neat formulation, the initial height of foam formed is reported along with the time for its disappearance. Formulation (% by weight):

2.93 DOWANOL DPM an oxypropylene adduct of methanol, available 0 from The Dow Chemical Company

1.4 DOWANOL DPnB an oxypropylene adduct of butanol, available from The Dow Chemical Company

1.54 Monoethanolamine

1.4 Nonionic surfactant, see Table II

1.2 linear alkyl benzene sulphonic acid

0.5 Coco Fatty acid

0.31 Citric acid monohydrate ⁵ 3.0 Trisodium Citrate

0.3 Magnesium Sulphate balance to 100% being deionized water.

0

5 Table II

Nonionic Comp. Comp. Comp. Comp. Com. Surfactant 1 2 3 4 A*

IPP Test (Neat Formulation)

90.5 91.7 91.3 90.4 89.9

% surface cleaned

IPP Test (1.5 wt% of formulation in tap water): 65.8 60.2 60.8 59.5 54.1

% surface cleaned

Foam Control cm cm cm cm cm

0 Sec 1.3 1.5 1.8 1.8 2.3 10 Sec 0.1 0.2 0.5 0.5 1.0 20 Sec / 0.1 0.4 0.3 0.5 30 Sec / 0.1 0.3 0.2 0.3 40 Sec / / / 0.1 60 Sec / / / 0.1 0.1 90 Sec / / / / 0.1

* Not an example of this invention

Example 5

As in Example 4, the value of the compositions of this invention as nonionic surfactants in a typical hard surface cleaner can be demonstrated. Atypical hard surface cleaner formulation is given below, the nonionic surfactant is as given in Table III. Comparative Surfactant C, representative of a typical commercially employed nonionic surfactant is

DOWFAX 20A64, an oxypropylene-oxyethylene adduct of a fatty alcohol, available from The Dow Chemical Company.

Formulation (% by weight):

3.0 DOWANOL DB an oxyethylene adduct of butanol, available from The Dow Chemical Company 2.6 Nonionic surfactant, see Table III

2.9 Sodium paraffin sulphonate

0.8 K Coco soap

0.7 Sodium hydrogen carbonate

0.1 Sodium chloride

1.1 Magnesium Sulphate balance to 100%, deionized water Table III

Nonionic

Surfactant Comp. 2 c*

IPP Test

(Neat

Formulation) 89.6 89.3

% surface cleaned

IPP Test

(1.5 wt% of formulation in

54.8 tap water): 53.8 0 % surface cleaned

Foam Control

(at pH 8) cm cm

0 11 9.5

1 Min 9.5 9

2 Min 5 8 5 33 MMiinn 22..55 7.5

4 Min 1.5 7

5 Min 1.3 6.5

* Not an example of this invention

Example6 0 Many cleaning formulations require the presence of a nonionic with an anionic surfactant to provide for an optimum performance. In such formulations it is frequently highly desirable to control and minimize foam formation and/or its persistence. This example demonstrates, by use of the above described modified Ross-Miles Test, the surprisingly good ability of the compositions of the invention to provide for foam control of a formulation -> comprising an anionic and nonionic surfactant.

0

5 Example Example Example Example pbw 6.1* 6.2 6.3* 6.4

Water 94.5 94.5 94.5 94.5

ANIONIC SURFACTANT:

DOWFAX 3B2 3.0 3.0 / /

Sodium Paraffin

/ / sulphonate 3.0 3.0

NONIONIC SURFACTANT:

DOWFAX 20A64 * 2.5 / 2.5 /

Composition 1 / 2.5 / 2.5

FOAM CONTROL: height (cm)

0 13.5 9 14.5 14.5

0.5 Min 12 6 14 12

1 Min 11.5 1.5 13.5 9 1.5 Min 11 1 13 8

2 Min 10.5 0.9 12.5 7.5

* Not an example of this invention

Anionic surfactant DOWFAX 3B2 is available from The Dow Chemical Company. Example 7

This example illustrates the value of the composition of this invention as a foam control agent in the food industry.

At room temperature, into a 1 weight percent solution of milk powder in water, further containing 10 ppm of a foam control agent, an air stream is introduced with agitation to produce a foam. The time taken for the foam to rise to the top of the vessel is measured. The air supply is then switched off, agitation stopped, and the time taken for the foam to collapse measured.

Foam

Foam Control Foam rise Collapse

Agent time (sec) time (sec)

/ 20 140

Dowfax DF-115 * 195 40

Composition 6 >300 40

* Not an example of this invention Composition 6 retards most effectively foam formation and also provides for an attractive, short, dispersion time of foam should it accumulate. Composition 6 is obtained according to the general procedure of Example 1 by reacting an alkoxylated fatty alcohol represented bythe formula C-oO-(C₂H4θ-)gH with 0.94 mole equivalents of isobutyl vinyl ether. The resulting composition contains 6 weight percent alkoxylated fatty alcohol and 94 weight percent of an acetal composition; the acetal composition being constituted by 43.9 weight percent Acetal-1, 50.6 weight percent Acetal-ll and 5.5 weight percent Acetal-lll. Composition 6 exhibits a cloud point temperature of 15°C.

Foam control agent DOWFAX DF-1 15, available from The Dow Chemical Company, is representative of such agents as presently used in the industry for this purpose.

The examples presented hereinabove clearly demonstrate that the compositions of the invention have an enhanced surface activity; exhibit similar or improved cleaning performance; exhibit a highly desirable degree of biodegradability; and exhibit a good degree of foam control.

Claims

Claims : _ _ . . . . . ,

1. A composition comprising a hydroxyl-terminated polyoxyalkylene and an acetal or ketal characterized in that the: a) the acetal or ketal, present in an amount of from 1 to 99 percent by weight based on total parts by weight of the composition, is an adduct of a monohydroxyl-terminated polyoxyalkylene; and b) the composition exhibits a critical micelle concentration (CMC) in water of less than 25 ppm of water at 25°C.

2. The composition of Claim 1 containing an acetal and wherein said acetal is a mixture which, based on total parts by weight of all acetal present, comprises: a) from 1 to 99 weight percent of a substance corresponding to Formula (I):

F - (AO)_n - 0 - CH - 0 - (AO)n - F

I (I)

CH₃ and b) from 99 to 1 weight percent of a substance corresponding to Formula (II):

F - (AO)n - 0 - CH - O - R I (ID;

CH₃ wherein F is independently a hydrocarbyl radical having from 6 to 30 carbon atoms; AO is independently a C₂_4 oxyalkylene moiety; n is independently a number of from 3 to 30; and R is a hydrocarbyl radical having from 1 to 5 carbon atoms.

3. A fatty alcohol alkoxylate composition that contains from 1 to 99 parts per 100 parts by total weight of the composition of an acetal mixture comprising components (a) and (b) wherein said mixture is characterized in that, based on the total parts by weight of (a) and (b) present, it comprises: a) from 1 to 99 weight percent of a substance corresponding to Formula (I); and F - (AO)_n - O - CH - O - (AO)n - F

I (0

CH₃ b) from 99 to 1 weight percent of a substance corresponding to Formula (II):

F - (AO)n - 0 - CH - O - R

I (ID

4. The composition of Claim 2 or 3 which further comprises, (c) a substance corresponding to Formula (III):

R - O - CH - O - R

I (IN);

CH₃ wherein R is is a hydrocarbyl radical having from 1 to 5 carbon atoms, and which is present, based on total parts by weight of all acetal present, in from 0.1 to 15 weight percent.

5. A process for preparing a composition, according to Claim 2 or 3, characterized in that a monohydroxyl-terminated polyoxyalkylene or fatty alcohol alkoxylate is reacted, in the presence of an acid catalyst, with an alkyl vinyl ether present in an amount to provide from 0.05 to 0.98 equivalents per hydroxyl group.

6. A method for stabilizing oil or gas well walls which comprises using an invert-emulsion or emulsion drilling mud wherein the invert-emulsion drilling mud contains from 0.5 to 100 percent by weight, and the emulsion drilling mud contains from 0.5 to 50 percent by weight, of a composition according to Claim 1, 2, 3 or 4.

7. A method for dispersing oil spills on water which com prises treating an oil-contaminated water surface with a dispersing agent comprising a composition according to Claim 1, 2, 3 or 4.

8. A method for controlling foam formation of an aqueous or non aqueous mixture in an environment with free surface turbulence which comprises bringing said mixture into contact with from 0.0001 to 10 percent by weight of a composition according to Claim 1, 2,

3 or 4.

9. A method to mercerize textile threads which comprises treating the textile thread with a caustic solution in the presence of a composition according to Claim 1, 2, 3 or 4.

10. A formulation which comprises a composition according to Claim 1 , 2, 3 or

4 for use as a cosmetic agent, a cleaning agent, an oil dispersant, a foam controllant, a lubricant or a mercerizing agent.

11. A formulation which comprises a composition according to Claim 1 , 2, 3 or 4, and an active component being a herbicide, insecticide, fungicide, bactericide, or a physiologically active substance.