DI-SUBSTITUTED SURFACTANT PRECURSORS AND DERIVED SURFACTANTS This invention is for di-substituted surfactant precursors and surfactants prepared from them, methods of making the di-substituted surfactant precursors and derived surfactants.

In one aspect, this invention relates to the production of di-substituted surfactant precursors. It is well known in the art that a, p-diols and a, ß-di-substituted compounds may be prepared by the ring opening of substituted three member heterocyclic rings such as pentane-1, 2-oxide. Thus pentane-1, 2-diol may be prepared by the acid catalyzed hydrolysis of 1, 2-epoxy pentane [see, Sandler & Karo, Organic Functional Group Preparation, Vol. 1, p104]. Further, it is well known in the art that hydrophobic epoxides (substantially insoluble in water, and whose hydrolysis products are substantially insoluble in water) that yield hydrophobic diol compounds can only be completely hydrolyzed in aqueous systems containing an organic co-solvent. It is also known in the art that the hydrolysis of substantially water-insoluble epoxides in water is generally incomplete, or difficult to drive to completion (hydrolysis may, for example, require temperatures in excess of 100 degrees Celsius and/or very long reaction times to ensure completion of reaction), and, further, that ethers, rather than the desired diol, may be the substantive product. It is desirable to be able to hydrolyze hydrophobic epoxides in water in the absence of any added organic co-solvent, at temperatures lower than 100 degrees Celsius and pressures less than or equal to one atmosphere. It is further desirable to be able to obtain diol compounds from that hydrolysis which contain controlled levels of diol and ether by-products in the diol product mixture.

In another aspect this invention relates to surfactants prepared from the precursors.

Surfactants based on linear alcohols (e. g. , linear alcohol alkoxylates, alkyl sulfates and alkyl ether sulfates) have been used successfully in detergent formulations in the past.

These surfactants have acceptable surfactant properties and are readily biodegradable.

However, recently, liquid dishwashing detergents, liquid laundry detergents, and powdered laundry detergents have all been offered to the consumer at significantly higher surfactant concentrations than traditionally. In this regard, a modern laundry detergent provides surfactant in about 3 ounces (88.72 ml) of detergent material, compared to an equivalent laundry detergent as provided in 1 cup (236.6 ml) of detergent material in the 1970s; the concentration of the surfactant in today's detergent is commensurately about 30% greater than was the case in the 1970s. These higher concentrations along with changes in washing temperatures [the average wash temperature in the 1970s was about 105 degrees F (40.5 °C) as compared to an average modern wash temperature of about 95 degrees F (35 °C)] establish a set of criteria which must be acceptably resolved by the modern surfactant molecule of choice. In meeting these criteria, traditional surfactants (based on linear alcohols) are frequently modified with additives to provide acceptable aqueous solution properties. In this regard, linear alcohol-based surfactants have a room- temperature viscosity well above 10,000 centipoise, where a maximum of about 300 centipoise in a liquid detergent is needed for utility in the normal laundry application. In resolving this viscosity problem, solvents (such as ethanol and propylene glycol) are added to many liquid laundry detergent formulations to lower the solution viscosity to an acceptable level. In agglomerated powdered detergent processes there is a need today for highly active and pumpable surfactant pastes (greater than 80% surfactant by weight) to minimize energy costs associated with removing excess water. These criteria can not be conveniently satisfied using surfactants based on linear alcohols (due to unfavorably high aqueous solution viscosities). In the case of powdered detergents, the situation is further complexed insofar as lower wash temperatures, as referenced above, effect slower dissolution rates of the powdered surfactant into wash water, especially insofar as the traditional method of spray drying a powder has given way (in consideration of the increased level of active ingredients in powdered detergents) to use of agglomeration, which does not provide a particle having comparable porosity to a spray-dried powder particle.

As noted above, surfactants known to the art have serious deficiencies in their aqueous solution properties, thus limiting their usefulness in highly concentrated formulations. For example, linear alcohol ethoxylates having hydrophobic groups of about 12 carbon atoms or more have low critical micelle concentrations, a desirable property in surfactants.

However, linear alcohol ethoxylates also exhibit broad gel regions (viscosity greater than 10,000 cps) when mixed with water. Generally these gel regions begin at around 30 weight percent surfactant and continue at concentrations of greater than 80 weight percent of surfactant (see, Shell Chemical Company, Neodol Ethoxylate and competitive Nonionics Properties Guide, 1994). This property limits the amount of surfactant capable of being incorporated into the final product, unless large amounts of solvents (such as ethanol and propylene glycol) are used. Linear alcohol ethoxylates with hydrophobic groups of about 10 carbon atoms or less mitigate, to some extent, the broad gel regions, but have undesirable odors associated with them. In addition, surfactants based on these shorter hydrophobes have relatively high critical micelle concentrations. Surfactants with high critical micelle concentrations have low effectiveness, thus limiting their use in many detergent applications. This is especially true in liquid laundry detergents and liquid hand dishwashing detergents where a small amount of product is diluted with copious amounts of water. Secondary alcohol ethoxylates having hydrophobic groups of about 12 carbon atoms or more have properties that fall somewhere between. That is, these surfactants offer a compromise between these properties but do not address the deficiency adequately.

Recently, there has been a significant amount of interest in mid-chain branched surfactants. These reportedly overcome, to some extent, the aforementioned solution deficiencies of surfactants based on linear alcohols without dramatically affecting biodegradation rates. Other enhanced properties such as narrow gel regions, improved low temperature detergency, increased tolerance to divalent cations, and greater formulation stability (enabling increased levels of builders and other formulation ingredients) have been reported (see, for example, U. S. Patent No. 6,150, 322; U. S. Patent No. 6,093, 856 ; International Patent Publication WO 99/19450; International Patent Publication WO 99/19437; and International Patent Publication WO 99/19440). But, there continues to be a need for surfactants that (a) have low critical micelle concentrations and yet (b) are not prone to experience broad gel regions when mixed with water. The present invention provides a solution to this need. In one aspect, the present invention concerns a di-substituted surfactant precursor compound represented by the following formula r'R''nR''' I wherein R'is R"independently is Rill is n is an integer having a value between 0 and 20; Ra is, independently, R'XZ, R1Z, R1X, or R1 where Ra has between 4 and 30 carbon atoms; Rl is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group; Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like; G is, independently, R3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and X is, independently, (CONTINUED ON NEXT PAGE) with the proviso that the total number of carbon atoms in the compound is at least 6n+12 ; and with the proviso that where R'R''nR''' is not a compound of formula II wherein R° is n-CloH21 ; and any mixture thereof.

In another aspect, the present invention concerns a blend of at least one compound of formula R'R"nR"' (formula I) as described hereinbefore with a compound of formula II wherein Rc is n-C10H21; and any mixture thereof In another aspect, the present invention concerns a blend of between 0.1 weight percent and 99.9 weight percent of a a, p-di-substituted compound having the following formula III wherein Rb is, independently, XZC, ZC, XC, or C, and X, Z, Rl, R3, and G are as defined hereinbefore and, and, as the reminder, at least one di-substituted surfactant precursor compound having the formula R'R"nR"' (formula I) wherein R', R", R"'and n are as defined hereinbefore.

In another aspect, the present invention concerns a method for preparing the above di- substituted surfactant precursor compounds of formula R'R"nR"' (formula 1) wherein R', R", R"'and n are as defined hereinbefore which method comprises the steps of : (a) admixing (i) a substituted three-membered heterocycle compound having between 6 and 32 carbon atoms selected from the group consisting of a substituted 1- oxacyclopropane, a substituted 1-thiacyclopropane, and a substituted 1- azacyclopropane, (ii) water in at least 50% molar proportion to the heterocycle compound, (iii) surfactant in sufficient weight percentage to achieve dispersion of the heterocycle compound within the water as an emulsion, and (vi) hydrolysis catalyst; and (b) sustaining an emulsion admixture of the resulting di-substituted surfactant precursor, the water, the heterocycle compound, the surfactant, and the catalyst so that the heterocycle compound and water convert to the di-substituted surfactant precursor.

The amount of heterocycle compound is not critical to the practice of the process of this invention. A suitable amount of the heterocycle compound to be used in this process would be readily known to a person of an ordinary skill in the art and would, in general, depend on the size of the reaction vessel used. Typically, the amount of heterocycle compound would be from about 1 to about 70, preferably from about 2 to about 50, most preferably from about 2 to about 25, percent by weight.

Still in another aspect, the present invention concerns a surfactant made through treating the di-substituted surfactant precursor compound of formula R'R"nR" (formula I) obtained in the above described process by additional steps of : (a) removing essentially all water from the admixture to provide residual anhydrous di-substituted intermediate; and (b) hydrophilicizing the anhydrous di-substituted surfactant intermediate to derive the surfactant product.

Conveniently, the di-substituted surfactant precursor compound employed in the above mentioned process for the preparation of the surfactant product can be either di-substituted precursor compound of formula I hereinbefore, a blend of two or more di-substituted precursor compounds of formula I hereinbefore, a blend of at least one di-substituted precursor compound of formula I hereinbefore and a, 0-di-substituted compound of formula III hereinbefore, or a blend of two or more a, ß-di-substituted compound of formula III hereinbefore.

In another aspect, the present invention concerns a surfactant comprising a compound having the following formula R'R''nR''' IV wherein R'comprises R"independently comprises R"'comprises n is an integer having a value between 0 and 20; J is, independently, any of S03M, PO (OM) 2, ZC02M, H, an alkoxylene monomeric unit having between 2 to 4 carbon atoms or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms or any mixture thereof, an alkoxylene monomeric unit having between 2 to 4 carbon atoms wherein said alkoxylene is capped with a functional group selected from the group consisting of SO3M and PO (OM) 2 and ZCO2M and H or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms and wherein said polyalkoxylene is capped with a functional group selected from the group consisting of SO3M and PO (OM) 2 and ZC02M and H or any mixture thereof, wherein M is either a monovalent cation, for example, sodium, potassium, ammonium and Cl 24 alkylammonium cation, or H and with the proviso that not all J are H; Ra is, independently, R'XZ, RlZ7 RlX or Rl with the proviso that Ra has between 4 and 30 carbon atoms; Rl is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group; Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like; G is, independently, is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl isopropyl and the like; and X is, independently, with the proviso that the total number of carbon atoms in said compound is greater than or equal to 6n+12 ; and with the proviso that R'R''nR''' is not a compound of formula IV above wherein Rc is n-Cl0H2l ; or a blend of two or more compounds of formula R'R"nR"' (formula IV) wherein R', R", R"'and n are as defined in above.

Still in another aspect, the present invention concerns a surfactant blend of at least one compound having formula IV as described hereinbefore with a compound of formula V wherein R° is n-CloH21 and J is defined as hereinbefore.

Still in another aspect, the present invention concerns a surfactant blend of between 0.1 weight percent and 99.9 weight percent ofana, P di-substituted compound having formula VI with a compound of formula R'R"nR"' (formula IV above), in essential remainder, wherein (CONTINUED ON NEXT PAGE) R'is R"independently is R'"is n is an integer having a value between 0 and 20; J is, independently, any of S03M, PO (OM) 2, ZCO2M, H, an alkoxylene monomeric unit having between 2 to 4 carbon atoms or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms or any mixture thereof, an alkoxylene monomeric unit having between 2 to 4 carbon atoms wherein said alkoxylene is capped with a functional group selected from the group consisting of SO3M and PO (OM) 2 and ZC02M and H or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms and wherein said polyalkoxylene is capped with a functional group selected from the group consisting of S03M and PO (OM) 2 and ZCOaM and H or any mixture thereof, wherein M is either a monovalent cation, for example, sodium, potassium, ammonium and Cl 24 alkylammonium cation, or H and with the proviso that not all J are H for at least 70 percent of all molecules in said blend; Ra is, independently, RlXZ, R'Z, RlX, or Rl with the proviso that Ra has between 4 and 30 carbon atoms; Rb is, independently, XZC, ZC, XC, or C; Rl is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group; Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like; G is, independently, R3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and X is, independently, with the proviso that the total number of carbon atoms in each compound is greater than 6n+12.

Still in another aspect, the present invention concerns a surfactant having the following properties: (a) a critical micelle concentration of not greater than about 0.005 weight percent of the surfactant in water when admixed with water at about 25 degrees C; (b) an aqueous solution viscosity of less than 2500 centipoise for all admixtures of the surfactant in water when admixed with water at about 25 degrees C; and (c) light transmittance greater than about 75 percent for all admixtures of the surfactant in water when admixed with greater than about 90 weight percent of water at about 23 degrees C where the light is of about 650 nm wavelength and the sample path length is about 2.0 cm.

This invention uses a process of hydrolyzing a substituted three-membered heterocycle having between 6 and 32 carbon atoms (a substituted 1-oxacyclopropane, a substituted 1- thiacyclopropane, or a substituted 1-azacyclopropane ; preferably a hydrophobic epoxide having a Hildebrand solubility parameter between about 16.307 and about 16.924 (joules/cm3) l/2 such as hexylene oxide, octylene oxide, and the like). So, in one aspect, this invention is embodied as a process for hydrolyzing a hydrophobic epoxide in water to prepare a diol product that contains varying levels of diol and ethers. It has been discovered that the rate of the reaction and the ratio of diol to ether is efficaciously controlled by conducting the hydrolysis of the epoxide in water by adding a surfactant in an amount sufficient to disperse the epoxide in the water as an emulsion, and by adding a hydrolysis catalyst, such as, without limitation, H2SO4 or HC104, with stirring adequate to sustain this emulsion, and heating to temperatures less than or equal to 100 degrees Celsius. Without surfactant, the reaction is incomplete. With 5% Sodium Dodecyl Sulfate (SDS) and H2SO4 as catalyst, the reaction yields 99% diol-ether product. The substitute three-membered heterocycle having between 6 and 32 carbon atoms is represented by the following formula: wherein Ra is, independently, R1XZ, RIZ, R'X, or Rl with the proviso that Ra has between 4 and 30 carbon atoms; R1 is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group; Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like; G is, independently, R3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and X is, independently, (CONTINUED ON THE NEXT PAGE) Non-limiting examples of the hydrocarbon group contemplated by the substituent Ri in the above described formulae are n-octyl, 1, 1, 1-trimethylpentyl, n-decyl, n-dodecyl, n- tetradecyl, n-hexadecyl, n-dodecyl, and the like.

Non-limiting examples of the hydrocarbylene group contemplated by the substituent Z in the above described formulae are methylene, ethylene, 1, 2-propylene, 1,3-propylene, 1,4- butylene, and the like.

Non-limiting examples of the hydrocarbyl group contemplated by the substituent R3 in the above described formulae are methyl, ethyl, n-propyl, n-butyl, iso-propyl, isobutyl, tertiary-butyl, and the like.

In another aspect of this invention, the diol mixtures formed above may be hydrophilized (i. e. further reacted to add a hydrophilic group) to form surface active agents that have been found to have surprising and useful properties. The hydrophilicization step may include, without limitation, alkoxylation, sulfation, phosphation, or carboxylation.

Alkoxylation of a diol product is achieved by methods known in the art, for example, by adding a base catalyst to the diol product, removing substantially all water, and then reacting with an organic epoxide or any combination of organic epoxides. Non-limiting examples of organic epoxides useful in the present process are ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO). Sulfation may be achieved by reaction with CIS03H or S03 reagents, as is well known in the art. Phosphation may be achieved by reaction with P205 or anhydrous H3PO4 as is known in the art. Carboxylation may be achieved by reacting the diol mixture in the presence of a base with chloroacetic acid, for example. The polyalkoxylene-hydrophilicized diol product may be converted to an anionic product by further reaction of the diol mixture polyalkoxylene ether to form a sulfate, phosphate, or carboxylate.

These surfactants are alternatively monomeric surfactants, mixtures of monomeric and polymeric surfactants, or polymeric surfactants. Surprisingly, the inventors have discovered surfactants that have low critical micelle concentrations yet do not experience broad gel regions when mixed with water. This novel property circumvents the limitations of surfactants known to the art. These surfactants include, without limitation, sulfates, alkoxylates, polyalkoxylates, phosphates, carboxylates, and sulfates, carboxylates and phosphates of alkoxylates or polyalkoxylates or mixtures thereof.

The following examples are provided to more fully illustrate the present invention but are not intended to be, nor should they be construed as being, limiting in any way of the scope of the invention.

Example 1 Hydrolysis of tetradecane-1, 2-oxide : 700 mL deionized (DI) H20 were heated to 88-90 °C in a stirred reactor, with agitation (stir at 2000 rpm). An emulsion composed of 30 g DI H2O, 0.7 g sodium lauryl sulfate (SLS), and 14.0 g tetradecane-1, 2-oxide was added, followed by 0.7 mL conc. H2SO4. After 1 hour a sample was taken. Supercritical Fluid Chromatography (SFC) analysis of the diluted sample showed complete consumption of the starting material, and formation of 1,2-tetradecanediol and ethers derived from that diol (-68 : 32 mass ratio by SFC analysis).

Comparative Example 1 The process of Example 1 was repeated except that tetradecane-1, 2-oxide was added neat, without surfactant. After 4 hours, as sample was taken. SFC analysis of the diluted sample showed incomplete consumption of the starting material, and formation of some 1,2- tetradecanediol and ethers derived from that diol (-81 : 13: 0.75 mass ratio oftetradecane-1-2- oxide to 1-2-tetradecanediol to ethers respectively by SFC analysis).

Comparative Example 2 Hydrolysis of hexene-1, 2-oxide : the process of Example 1 was repeated except hexene oxide was used as the substrate. After 4 hours, a sample was taken. GC analysis showed that the epoxide was largely consumed, and that the diol was formed (-90 diol: 5 hexene mass ratio by SFC analysis). SFC analysis showed trace levels of ethers (<<1%).

Example 2 Hydrolysis of hexadecane-1, 2-oxide: A clear microemulsion composed of water (8. 4g), Oleth-10 (1.05 g), and hexadecane-1, 2-oxide (0.53 g) was formed by mixing the components.

190 mg concentrated H2SO4 were added at room temperature, and mixed. The epoxide was 99% consumed in a few minutes to yield 1,2-hexadecanediol (99% selectivity).

Example 3 Hydrolysis of dodecane-1, 2-oxide: An emulsion formed of 12.0 g dodecane-1, 2-oxide and 6.0 g dodecane-1, 2-diol 12-ethoxylate in 108 g water was stirred at 70 °C. 1.0 mL 1 M H2SO4 was added and in 2 hours, the starting epoxide was 97% consumed, as determined by gas chromatography (GC) analysis. The product consisted of dodecane-1, 2-diol and diol ethers in a 75: 11 mass ratio by SFC analysis.

Example 4 Ethoxvlation of dodecane-1 2-diol : Into a 2 gallon stirred reactor were loaded 2564 g dodecane-1, 2-diol and 2. 85 g KOH. The mixture was heated and stirred under vacuum at 130 °C to remove the residual water to a level of 62 ppm. 1710 g ethylene oxide were then added over 4 hours, followed by reaction for 2 more hours at 130 °C. 1800 g dodecane-1, 2-diol-3.3- ethoxylate were drained from the reactor. 870 g EO were added to the reactor as above. 1116 g dodecane-1, 2-diol-6-ethoxylate were drained from the reactor. 620 g more EO was added as above, and 1133 g dodecane-1, 2-diol-9.4-ethoxylate were drained from the reactor. 330 g more EO were added as above, and 1149 g dodecane-1, 2-diol-11. 8-ethoxylate were drained from the reactor. 175 g more EO were added, and reacted as above, to yield 1061 g dodecane- 1, 2-diol-18. 9-ethoxylate.

Example 5 Ethoxvlation of tetradecane-1, 2-diol : Into a 2 gallon stirred reactor were loaded 2733 g tetradecane-1, 2-diol and 2.82 g KOH. The mixture was heated and stirred under vacuum at 130 °C to remove the residual water to a level of 999 ppm. 1595 g ethylene oxide were then added over 2 hours, followed by reaction for 0.5 more hours at 130 °C. 1702 g tetradecane- 1, 2-diol-3.2-ethoxylate were drained from the reactor. 795 g EO were added to the reactor as above. 1102 g tetradecane-1, 2-diol-5.7-ethoxylate were drained from the reactor. 730 g more EO was added as above, and 1082 g tetradecane-1, 2-diol-8.4-ethoxylate were drained from the reactor. 525 g more EO were added as above, and 1088 g tetradecane-1, 2-diol-13. 4- ethoxylate were drained from the reactor. 125 g more EO were added, and reacted as above, to yield 1529 g tetradecane-1, 2-diol-16. 6-ethoxylate.

Example 6 Sulfation of dodecane-1. 2-diol-3. 3-ethoxylate : To a nitrogen flushed, cooled (ice bath) 3- neck round bottomed flask equipped with a thermometer, addition funnel, condenser, and stir bar, was added 100.0 g dodecane-1, 2-diol-3. 3-ethoxylate and 100 mL dry CH2Ck. The solution was stirred. 90 mL dry CH2Cl2 and 28.9 g liquid S03 were added to the addition funnel. 84 mL of this was added dropwise to the reaction flask while maintaining the temperature of the reaction flask at 6-9 °C. After completion of addition, the reaction was allowed to warm to room temperature over 2 hours. The CH2C12 was evaporated and 140 mL DI H20 and 48.0 mL 5 N NaOH were added. The solution was neutralized to pH 9 with NaOH. (In both cases, 3 x 50 mL methanol was then added (repeatedly) to the aqueous solution and the solvents were evaporated under reduced pressure to yield a pale yellow oil (136. 9 g).

Example 7 Sulfation of dodecane-1, 2-diol-3. 3-ethoxylate : To a nitrogen flushed, cooled (ice bath) 3- neck round bottomed flask equipped with a thermometer, addition funnel, condenser, and stir bar, was added 20.0 g dodecane-1, 2-diol-3.3-ethoxylate and 90 mL dry CH2C12. The solution was stirred. 90 mL dry CH2C12 and 10.65 g liquid S03 were added to the addition funnel.

This solution was added dropwise over 4.5 hours to the reaction flask while maintaining the temperature of the reaction flask at 6-9 °C. After completion of addition, the reaction was allowed to warm to room temperature. The CH2C12 was evaporated and 20 mL DI H20 and 21. 1 mL 5 N NaOH were added. The solution was neutralized to pH 9 with NaOH. (In both cases, 3 x 100 mL ethanol was then added (repeatedly) to the aqueous solution and the solvents were evaporated under reduced pressure to yield an orange oil.

Example 8 Sulfation of tetradecane-1, 2-diol-3. 2-ethoxylate : To a nitrogen flushed, cooled (ice bath) 3- neck round bottomed flask equipped with a thermometer, addition funnel, condenser, and stir bar, was added 100.0 g tetradecane-1,2-diol-3. 2-ethoxylate and 100 mL dry CH2C12. The solution was stirred. 90 mL dry CH2C12 and 22.5 g liquid S03 were added to the addition funnel. This solution was added dropwise to the reaction flask over 4 hours while maintaining the temperature of the reaction flask at 6-9 °C. After completion of addition, the reaction was allowed to warm to room temperature over 2 hours. The CH2C12 was evaporated and 100 mL DI H20 and 44.0 mL 5 N NaOH were added. The solution was neutralized to pH 9 with NaOH. (In both cases, 3 x 100 mL methanol was then added (repeatedly) to the aqueous solution and the solvents were evaporated under reduced pressure to yield a viscous orange oil.

Example 9 Sulfation of tetraecane-1. 2-diol-3. 2-ethoxylate : To a nitrogen flushed, cooled (ice bath) 3- neck round bottomed flask equipped with a thermometer, addition funnel, condenser, and stir bar, was added 50.0 g tetraecane-1,2-diol-3. 2-ethoxylate and 60 mL dry CH2C12. The solution was stirred. 90 mL dry CH2C12 and 22.5 g liquid S03 were added to the addition funnel. This solution was added dropwise to the reaction flask over 2 hours while maintaining the temperature of the reaction flask at 6-9 °C. After completion of addition, the reaction was allowed to warm to room temperature over 2 hours. The CH2C12 was evaporated and 100 mL DI H20 and 44.0 mL 5 N NaOH were added. The solution was neutralized to pH 9 with NaOH. (In both cases, 3 x 100 mL methanol was then added (repeatedly) to the aqueous solution and the solvents were evaporated under reduced pressure to yield a viscous oil.

Example 10 Hydrolysis of dodecane-1, 2-oxide : 600 mL DI H20 were heated to 90 °C in a stirred reactor, with agitation (stir at 2000 rpm). An emulsion composed of 200 g DI H20, 5.0 g sodium lauryl sulfate, and 100.0 g dodecane-1, 2-oxide was added, followed by 0.94 mL conc. H2SO4.

After 1 hour a sample was taken. SFC analysis of the diluted sample showed complete consumption of the starting epoxide, and formation of 1,2-dodecanediol and ethers derived from the reaction of that diol with the epoxide starting material, as well as the products of the subsequent reaction of these derived ethers with the starting epoxide. The reaction was allowed to continue for 5 hours. This reaction was repeated 6 times, and the products combined. After cooling, each reaction mixture was poured into a 2 L separatory funnel with 300 mL ethyl acetate and 25 g NaCl were added. The aqueous layer was removed, and the next reaction mixture was added and separated similarly. The organic layer was washed with 4 x 100 mL 0.5 N NaOH, the 4 x 100 mL brine. The pH of the resulting final brine layer was 5-6. Solids that had separated out of the organic layer were filtered off and saved. The filtrate was dried over Na2S04 (anhydrous) and filtered. The initial filtrand was added back to the now dry ethyl acetate solution. The product was combined with the products of 2 smaller scale hydrolyses (each at 50 g dodecane-1, 2-oxide) and the solution rotovaped to dryness.

The composition of the resulting solid dodecanediol product was (diol: ethers) 40: 56 mass ratio by SFC analysis. The total mass recovered was 635 g (91% mass recovery).

Example 11 Ethoxylation, 2.7 EO: 181 g of the diol/ether product from Example 12 above were combined with 0.175 g KOH. 82 g EO were added at 140 °C and the reaction was heated and stirred at 140 °C for 14 h. After draining, the product was neutralized with acetic acid to pH=6.5, and determined to have an average of 2.7 EO units per unit. The CMC of a 1: 5 (w/w) mixture of this material and 1, 2-dodecanediol-6-ethoxylate (cloud point = 75 °C) was determined to be 0.005 wt% (compare to 0.01 wt% for 1, 2-dodecanediol-6-ethoxylate). No aqueous gel region was found across the entire dilution range (22 °C) for the mixture, compared to a gel region starting at 60 wt% for the 1, 2-dodecanediol-6-ethoxylate, and a gel region starting at 35 wt% for Neodol 23-9 (whose CMC is 0.003 wt%).

Example 12 Ethoxylation, 3.4 EO: 181 g of the diol/ether product from Example 12 above were combined with 0.26 g KOH.-170 g EO were added at 140 °C and the reaction was heated and stirred at 140 °C for 14 h. After draining, the product was neutralized with acetic acid to pH=7.6, and determined to have an average of 3.4 EO units per unit.

Example 13 Ethoxylation, 4.4 EO: 207 g of the diol/ether product from Example 12 above were combined with 0.26 g KOH. 3375 g EO were added at 140 °C and the reaction was heated and stirred at 140 °C for 14 h. After draining, the product was neutralized with acetic acid to pH=7.0, and determined to have an average of 4.4 EO units per unit. The CMC of a 2: 1 (w/w) mixture of this material and 1, 2-dodecanediol-9.4-ethoxylate (cloud point = 75 °C) was determined to be 0.002 wt% (compare to 0.01 wt% for 1, 2-dodecanediol-9.4-ethoxylate). Neither the 1,2- dodecanediol-9.4-ethoxylate or the mixture exhibited a gel point across the entire aqueous dilution range (22 °C), compared to a gel region starting at 35 wt% for Neodol 23-9 (whose CMC is 0.003).

Example 14 Physical properties (aqueous viscosity, Critical Micelle Concentration, Cloud Point) for alkane diol ethoxylates and alkane diol/alkane diol oligomer ethoxylate blends have been determined experimentally. Cloud Points were determined using a Mettler Model FP800 Thermosystem fitted with a FP81 measuring cell. Cloud points were determined at concentrations of 1 weight percent surfactant and were done in triplicate with the standard deviation <0. 2°C.

Aqueous viscosities were measured using a Brookfield Model DV-III Rheometer fitted with a small sample adapter. All measurements were taken at 23oC, at 3 rpm, using spindle number 18 unless noted. The viscosities listed are averages of four measurements. The term gel denotes a non-flowing, transparent liquid. The gels were not characterized further.

Critical micelle concentrations (CMCs) were measured using a Kruss Model K12 Tensiometer fitted with a Model 665 Dosimat for automation. All CMC's were determined at 25°C using the Wilhelmy Plate method. Values are from three consecutive measurements and the standard deviation is less than 0.1 dyne/cm.

Transmittance was used to quantify the transparency of the surfactant admixtures to ensure the admixtures made at ten weight percent surfactant are transparent single phase micellar solutions. Transmittance is defined at the ratio of the intensity of the transmitted beam (P) to the intensity of the incident beam (Po). The transmittance is reported as the % transmittance or (P/Po) x 100. All measurements were taken at 22°C using a Brinkman Model PC 910 Colorimeter fitted with a probe tip having a path length of 2 cm.

Measurements were done at a wavelength of 650 nm after calibrating the instrument against de-ionized water such that de-ionized water would have a transmittance of 100%.

The surfactant admixtures made at ten weight percent of surfactant were judged to be transparent single phase micellar solutions if they had % transmittance values of greater than 75%.

Table 1 summarizes the aqueous solution properties of selected important nonionic surfactant families along with examples of the preferred compositions. The nomenclature used for the surfactants of the current art is C-x-yEn where x and y denote the number of carbon atoms in the hydrophobic group and n denotes the average number of moles of ethylene oxide that has been condensed with each mole of hydrophobe. The inventive surfactants are surfactants A, B and C.

Surfactant A is an admixture of (a) 95% by weight of 1,2-dodecane diol ethoxylated to an average of about 5.5 moles of ethylene oxide and (b) 5% by weight of a polymeric di- substituted ether ethoxylated to an average of about 2.7 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.

Surfactant B is an admixture of (a) 90% by weight of 1,2-dodecane diol ethoxylated to an average of about 6 moles of ethylene oxide and (b) 10% by weight of a polymeric di- substituted ether ethoxylated to an average of about 2.7 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.

Surfactant C is an admixture of (a) 60% by weight of 1,2-dodecane diol ethoxylated to an average of about 9 moles of ethylene oxide and (b) 40% by weight of a polymeric di- substituted ether ethoxylated to an average of about 4.4 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.

In addition the CMC and cloud point is given for each surfactant. The cloud point is an important variable as it is an indicator of the hydrophilic/lipophillic nature of the surfactant. Similar cloud points indicate similar hydrophilic/hydrophobic properties and ensure that the comparisons between surfactants are meaningful.

Table 1 Aqueous Viscosities and Selected Surfactant Properties Concentration Primary Primary Secondary 1, 2-Alkane (wt. %) Alcohol Alcohol Alcohol Diol Surfactant A Surfactant B Surfactant C Surfactant Ethoxylate Ethoxylate Ethoxylate Ethoxylate C9-10E8 C12-15E9 C11-15E9 C12-14E6 20 6 8 6 5 5 5 5 30 26 70 40 14 15 14 14 40 130 Gel 260 76 68 67 77 50 Gel Gel Gel Gel 190 210 290 60 Gel Gel 320 Gel 330 230 310 70 130 9300 Gel 240 220 180 220 80 93 200 140 150 130 140 170 CMC 0.03 0.003 0.005 0.004 N/D 0.005 0.002 (wt%) Cloud 80 74 60 78 76 76 77 Point (C) As is demonstrated by the data in Table 1, the compositions give both low critical micelle concentrations and low aqueous solution viscosities across the entire dilution range. The low viscosity property is also observed with sodium salts of sulfated 1, 2-alkanediol ethoxylates.

Example 15 Table 2 lists aqueous viscosity data for selected surfactants. The surfactants are based on 1,2-alkane diols having an average of three moles of ethylene oxide of examples 8-11. The terms MS and DS denote mono-sulfate and di-sulfate. The commercial product is a sodium salt of a mono-sulfated lauryl alcohol ethoxylate having an average of two moles of ethylene oxide.

Table 2 Aqueous Solution Viscosities for Selected Sulfated 1,2-Alkanediol Ethoxylates Concentration 1, 2-Dodecanediol 1, 2-Dodecanediol 1, 2-Tetradecanediol 1, 2-Tetradecanediol Commercial (wt. %) Ethoxylate (3) MS Ethoxylate DS Ethoxylate MS Ethoxylate DS Sulfate Alcohol Ethoxylate 10 <5 <5 <5 <5 <5 20 &lt;5 <5 <5 <5 37 30 9 <5 14 5 25,000 40 36 5 280 13 N/D 50 290 11 Gel 55 N/D 60 Gel 29 N/D N/D N/D Example 16 The importance of the low solution viscosity properties is further demonstrated by incorporating the preferred compositions into prototype liquid laundry detergents.

Formulations were prepared with surfactants of the instant invention as shown in Table 3 where (a) Surfactant 1 is a mixture of (1) about 60% by weight of 1,2-dodecane diol ethoxylated to an average of about 9 moles of ethylene oxide and (2) about 40% by weight of a polymeric di-substituted ether ethoxylated to an average of about 4.4 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C and (b) Surfactant 2 is a mixture of (1) about 60% by weight of the di-sodium salt of 1,2-dodecanediol ethoxylated to an average of about three moles of ethylene oxide capped with about two sulfate groups and (2) about 40% by weight of the di-sodium salt of a polymeric di- substituted ether ethoxylated to an average of about 2.7 moles of ethylene oxide capped with about two sulfate groups.

Table 3 Component Weight % ABC Alcohol ether sulfate (2 moles EO) 20.1 20.1 16.1 Dodecylbenzene sulfonic acid sodium salt 6.1 6.1 6.1 Linear alcohol ethoxylate (C12-15E9) 4. 0-------- Surfactant 1----4. 0 4.0 Surfactant 2--------4. 0 Ethanol 2.3 2.3 2.3 Propylene glycol 3.5 3.5 3.5 Citric acid 1.7 1.7 1.7 Fatty acid 2.5 2.5 2.5 5N Sodium hydroxide (pH=8-9) 8.5 8.5 8.5 D. I. Water 51.3 51.3 51.3 Viscosity 22°C (cps) 1130 735 610 By design, the above compositions have a relatively low level of ethanol and propylene glycol. These solvents are generally added to reduce the product viscosity that arises from the deficiencies in surfactants used in commercial practice. Composition A contains only commercial surfactants known to the art. Compositions B and C are prepared by substituting surfactants of the invention for their commercial counter parts. Even when the detergent compositions are prepared with small amounts of the inventive surfactants, the formulation viscosity is significantly reduced, eliminating the need for additional solvents.

These very attractive solution properties coupled with low solidification temperatures (pour points) make attractive alternatives to existing surfactants in many applications such as liquid laundry detergents, hand dish detergents and hard surface cleaners. Indeed, the above shows that a new surfactant product is provided by the invention affording a new combination of aqueous admixture CMC, viscosity, and clarity properties according to the detailed features of : a critical micelle concentration of not greater than about 0.005 weight percent of said surfactant in water when admixed with water at about 25 degrees C; an aqueous solution viscosity of less than 2500 centipoise for all admixtures of said surfactant in water when admixed with water at about 25 degrees C; and light transmittance greater than about 75 percent for all admixtures of said surfactant in water when admixed with greater than about 90 weight percent of water at about 23 degrees C wherein the source of said light provides light of about 650nm wavelength and wherein a 2.0 cm sample path length of said surfactant in water is provided.

Improved solution properties also provide for high active, liquid laundry detergents and high active, stable, pumpable and transportable surfactant pastes used in powdered detergents (reference US Patent 6,294, 513, International Patent Publication WO 99/19453, International Patent Publication WO 99/19455, and International Patent Publication WO 99/19454). The improvements are believed to be the result of the small branches, (predominantly methyl, ethyl, and propyl branches) which presumably disrupt surfactant packing efficiencies. The small branches, while having an impact on surfactant solution properties, do not appear to have a major impact on biodegradation rates. These improvements provide surfactants having higher hydrophobicity than provided by surfactants derived from linear alcohols.

With the benefit of the description provided herein, it is expected that the described diol- based surfactants will provide improved performance in many applications when compared to mid-chain-branched surfactants. For example, when used in liquid formulations, the described diol-based surfactants should provide a lower formulation viscosity, thereby enabling (a) reduction or elimination of added solvents and (b) reduction in nonionic surfactant concentration.

The described diol-based surfactants also provide distinct advantages over surfactants based on linear and mid-chain-branched alcohols when either shorter chain surfactants or surfactants having enhanced hydrophilic properties are desired. These advantages derive from the extremely low levels of free diol in the alkoxylated product as compared to higher levels of free alcohol in the linear (or mid-chain-branched) alcohol alkoxylates. Linear alcohol ethoxylates having 3 moles of ethylene oxide and linear alcohol ethoxylates having 6 moles of ethylene oxide contain approximately 32% and 9% free alcohol, respectively. However diol ethoxylates having 3 moles of ethylene oxide and diol ethoxylates containing 6 moles of ethylene oxide contain approximately 8% and less than 1% free diol, respectively. This facilitates better transfer of the surfactant to the interface since it does not have to compete with the alcohol.

This lower level of free diol should also be an advantage with respect to enzyme stability in liquid formulations. It is known that enzymes are more stable in alcohol ethoxysulfates than in alcohol sulfates. It is also known that low mole ethylene oxide linear alcohol ethoxylates (used for the production of linear alcohol ethoxysulfates) contain high levels of free linear alcohol. Therefore, upon sulfation, the resulting surfactant mixture will contain high levels of alcohol sulfate. Since the described diol-based surfactants contain much lower levels of free diol, surfactant mixtures resulting from the sulfation of the low- mole diol-based ethoxylates will contain much lower levels of diol sulfate. Therefore, it is expected that the ethoxysulfates based on the described diol-based surfactants should be more compatible with enzyme systems in liquid formulations.

The low odor of the diol itself when coupled with the low level of free diol found in the diol alkoxylates will also greatly reduce the odor of C8-C12 alkoxylates. This is especially important in household product applications where these odors are seen as negative product attributes. Due to the odor problem, detergent manufactures frequently utilize C12-C14 ethoxylates. The diol-based alkoxylates will allow manufacturers to utilize shorter-chain-length alkoxylates, which are more efficient hydrotropes. When this is combined with the enhanced properties of the described diol-based surfactants, significantly less surfactant should be needed as compared to surfactants based on linear alcohol ethoxylates or mid-chain branched ethoxylates.

Low-streaking surfactants are also known in the art. Examples of these are Alkyl Polyglycosides (Ref. Alkyl Polyglycosides, Technology, Properties and Applications; K.

Hill, W. von Rybinski, G. Stoll; VCH Publishing, 1996) and DOWFAX 3B2. It is believed that non-streaking surfactants are surfactants that do not experience gel regions at relatively high surfactant concentrations (>50% by weight. ). Thus, hard surface (or all purpose) cleaners and window cleaner formulations based on these surfactants have been commercialized. It is expected that surfactants based on diols will also be non-streaking surfactants and thus be applicable to hard surface cleaners.

In addition to the advantages of the diol-based surfactants in disrupting surfactant packing (based on the molecular architecture), the disclosed surfactants also afford a significant electrostatic advantage. In this regard, anionic and cationic surfactants derived from diol precursors have up to two charges per surfactant molecule, offering significant advantages over mono-valent ionic surfactant molecules. It is well known that anionic surfactants are very efficient at removing particulate soils such as dirt and clay. The anionic surfactant establishes a negative charge at the fabric/soil/water interface (creating a repulsive force on the particle, which is also negatively charged). Surfactants having two anionic groups per molecule should be more efficient at building up the electrical charge ; accordingly, fewer surfactant molecules should be needed, reducing amounts of surfactant required in the detergent formulation. The same argument applies with respect to cationic surfactants; thus, lower concentrations of cationic surfactants should also be enabled in fabric softener formulations.

It is also well known that anionic surfactants presently used in laundry detergents have very high critical micelle concentrations (CMC), necessitating use of auxiliary (nonionic or cation) surfactants in lowering the CMC of the detergent formulation. One advantage of the described diol-based anionic surfactants is that a surfactant can now be tailored to have both a low CMC and a low Kraft temperature (the temperature where the solubility of the anionic surfactant is equal to the CMC), reducing (or even eliminating) the need, for auxiliary surfactants in lowering the CMC of the detergent formulation.

One major disadvantage of monovalent anionic surfactants is their sensitivity to divalent metal ions. When the cation of a monovalent anionic surfactant is exchanged with a divalent metal cation, a much more hydrophobic surfactant is formed (the divalent cation has two hydrophobic groups attached). That is not the case for the described divalent anionic diol-based surfactants. Thus, tolerance for hardness ions should be significantly improved over anionic surfactants based on linear alcohols or mid-chain branched alcohols. This feature allows a much more hydrophobic anionic surfactant to be used without fear of surfactant precipitation in the presence of hardness ions. Lower levels of detergent builder should be required with these types of surfactants. Furthermore, increased levels of calcium (known co-factors for detergent enzymes) can be added to liquid laundry detergent formulations without detrimental effects.

Surfactants are also a key component in emulsion polymerization. There has been significant work on the use of diol-based surfactants in emulsion polymerization (US Patent 4,549, 002; US Patent 5,346, 973; and Japanese Patent 59145028). The properties of the diol surfactants provide for greatly improved handling properties as well as for improved properties in an emulsion polymer. The described diol-based surfactants should also provide similar benefits in emulsion polymer formulations.

Due to the use patterns of personal care products, the makers of shampoos, soaps, body washes, and other personal care products often utilize surfactants that have been shown to be mild and less irritating. Surfactants based on diols and similar structures based on other glycols have been reported to have low irritation properties (US Patent 3,427, 248 and Japanese Patent 61166894). These surfactants have been used in formulations that have been shown to provide high performance with low tissue irritation. It is expected that the described diol-based surfactants will have similar irritation profiles and will therefore be very suitable in personal care formulations and other applications that require mild surfactants.

Thus the benefits of the described diol-based surfactants will be very suitable for many applications. These include but are not limited to: liquid laundry detergents, powered laundry detergents, laundry detergent tablets, laundry detergent pouches, hard surface cleaners, laundry pretreaters, bathroom cleaners, paints, emulsion polymers, coatings, agricultural applications, fabric softeners, carpet cleaners, liquid soaps, shampoos, and other applications that utilize nonionic, anionic, cationic, and amphoteric surfactants.

An example to selectively illustrate, without limitation, specific teachings above is related to liquid laundry detergents. As previously noted, these products are now offered at higher surfactant concentrations than in the past. One important surfactant found in liquid laundry detergents is based upon ethoxylated linear alcohols having hydrophobic groups of about 12 to 14 carbon atoms or more. These surfactants have low critical micelle concentrations, a desirable property in surfactants. However, linear alcohol ethoxylates also exhibit broad gel regions (viscosity > 10,000 cps) when mixed with water. Generally, these gel regions begin at around 30 weight percent surfactant and continue at concentrations of greater than 80 weight percent of surfactant (Shell Chemical Company, NeodolEthoxylate and competitive Nonionics Properties Guide, 1994). This property limits the amount of surfactant incorporated into the final product, unless large amounts of solvents (such as ethanol and propylene glycol) are used. Linear alcohol ethoxylates with hydrophobic groups of about 10 carbon atoms or less mitigate, to some extent, the broad gel regions, but have relatively high critical micelle concentrations. Surfactants with high critical micelle concentrations have low effectiveness, thus limiting their use in many detergent applications (especially in liquid laundry detergents and liquid hand dishwashing detergents where a small amount of product is diluted with copious amounts of water).

Secondary alcohol ethoxylates having hydrophobic groups of about 12 carbon atoms or more have properties that fall somewhere between. Consequently, these surfactants offer a compromise between these properties, but they still do not address the deficiency adequately. There continues to be a need for surfactants that have low critical micelle concentrations, yet are not prone to experience broad gel regions when mixed with water; and the described diol-based surfactants should provide a solution to this need.

Finally, the surfactants of the current invention can be used to significantly modify the aqueous solution properties of surfactants known to the art as shown in the following Example 19.

Example 17 In this example, the viscosity of a commercially available alcohol ethoxysulfate was measured (Steol CS-230, Stepan Company, Northfield, IL). The commercial product is an aqueous solution containing about 30% by weight of surfactant. This product is compared to a mixture of lOg Steol CS-230,3g TDD-3 MS, and 7g of DI water. The resulting mixture is about 30% by weight of surfactant. Aqueous viscosities were measured at 23°C using a Brookfield Model DV-III Rheometer fitted with a small sample adapter. The viscosity of Steol CS-230 was measured at 3 rpm, using spindle number 18.

The viscosity of the DDD-3 MS was measured at 6 rpm using spindle number 18.

The viscosity of Steol 230 (30% aqueous solution of a linear alcohol ethoxysulfate) is 25, 000cps. The viscosity of a 1: 1 mixture, by weight of Steol 230 and TDD-3MS, a diol ethoxysulfate, (30% aqueous solution) is 90cps, where TDD-3 MS is the mono-sulfate of tetradecane diol having an average of three moles of ethylene oxide. The TDD-3 MS and the Steol 230 have previously been referenced herein.

The information provided herein can be conveniently modified by those of skill, once given the benefit of this disclosure, to achieve the utility of the present invention without departing from the spirit of the present invention. It should be understood that the description and discussion herein has been presented by way of enabling example and explanation and that the breadth and scope of the present invention is identified in accordance with the following claims and their equivalents.