Detergents for cold-water cleaning

FIELD OF THE INVENTION

The invention relates to detergents and cold-water cleaning methods, and in particular, to mid-chain headgroup or alkylene-bridged surfactants useful therein.

BACKGROUND OF THE INVENTION

Surfactants are essential components of everyday products such as household and industrial cleaners, agricultural products, personal care products, laundry detergents, oilfield chemicals, specialty foams, and many others.

Modern laundry detergents perform well in removing many kinds of soils from fabrics when warm or hot water is used for the wash cycle. Warmer temperatures soften or melt even greasy soils, which helps the surfactant assist in removing the soil from the fabric. Hot or warm water is not always desirable for washing, however. Warm or hot water tends to fade colors and may accelerate deterioration of the fabric. Moreover, the energy costs of heating water for laundry make cold-water washing more economically desirable and more environmentally sustainable. In many parts of the world, only cold water is available for laundering articles.

Of course, laundry detergents have now been developed that are designed to perform well in hot, warm, or cold water. One popular cold-water detergent utilizes a combination of a nonionic surfactant (a fatty alcohol ethoxylate) and two anionic surfactants (a linear alkylbenzene sulfonate and a fatty alcohol ethoxylate sulfate) among other conventional components. Commercially available cold-water detergents tend to perform well on many common kinds of stains, but they have difficulty removing greasy dirt, particularly bacon grease, beef tallow, butter, cooked beef fat, and the like. These soils are often deposited as liquids but quickly solidify and adhere tenaciously to textile fibers. Particularly in a cold-water wash cycle, the surfactant is often overmatched in the challenge to wet, liquefy, and remove these greasy, hardened soils.

Most surfactants used in laundry detergents have a polar head and a nonpolar tail. The polar group (sulfate, sulfonate, amine oxide, etc.) is usually located at one end of the chain. Branching is sometimes introduced to improve the solubility of the surfactant in cold water, especially for surfactants with higher chain lengths (C₁₄to C₃₀), although there is little evidence that branching improves cold-water cleaning performance. Moreover, even the branched surfactants keep the polar group at the chain terminus (see, e.g., U.S. Pat. Nos. 6,020,303; 6,060,443; 6,153,577; and 6,320,080).

Secondary alkyl sulfate (SAS) surfactants are well known and have been used in laundry detergents. Typically, these materials have sulfate groups that are randomly distributed along the hydrocarbyl backbone. The random structure results from addition of sulfuric acid across the carbon-carbon double bond in internal olefin mixtures, accompanied by double bond isomerization under the highly acidic conditions.

Recognizing the solubility limitations of conventional secondary alkyl sulfates in cold water, U.S. Pat. No. 5,478,500 teaches to combine them with optimum levels of an amine oxide surfactant and a linear alkylbenzene sulfonate.

Secondary alkyl sulfates have been produced in which the sulfate group resides at the 2- or 3-position of the alkyl chain (see, e.g., WO 95/16016, EP 0693549, and U.S. Pat. Nos. 5,478,500 and 6,017,873). These are used to produce agglomerated high-density detergent compositions that include linear alkylbenzene sulfonates, fatty alcohol sulfates, and fatty alcohol ether sulfates. Similarly, U.S. Pat. No. 5,389,277 describes secondary alkyl sulfate-containing powdered laundry detergents in which the alkyl chain is preferably C₁₂-C₁₈and the sulfate group is preferably at the 2-position.

Longer-chain (C₁₄-C₃₀) surfactants have been produced in which the polar group resides at a central carbon on the chain, but such compositions have not been evaluated for use in cold-water laundry detergents. For example, U.S. Pat. No. 8,334,323 teaches alkylene oxide-capped secondary alcohol alkoxylates as surfactants. In a few examples, the original —OH group from the alcohol is located on a central carbon of the alkyl chain, notably 8-hexadecanol and 6-tetradecanol. As another example, sodium 9-octadecyl sulfonate has been synthesized and taught as a surfactant for use in enhanced oil recovery (see J. Disp. Sci. Tech. 6 (1985) 223 and SPEJ 23 (1983) 913). Sodium 8-hexadecyl sulfonate has been reported for use in powder dishwashing detergents (see, e.g., JP 0215698).

Numerous investigators have studied a series of secondary alcohol sulfates in which the position of the sulfate group is systematically moved along the alkyl chain to understand its impact on various surfactant properties. For example, Evans (J. Chem. Soc. (1956) 579) prepared a series of secondary alcohol sulfates, including sodium sulfates of 7-tridecanol, 8-pentadecanol, 8-hexadecanol, 9-septadecanol, 10-nonadecanol and 15-nonacosanol (C29), and measured critical micelle concentrations and other properties. More recently, Xue-Gong Lei et al. (J. Chem. Soc., Chem. Commun. (1990) 711) evaluated long-chain (C21+) alcohol sulfates with mid-chain branching as part of a membrane modeling study.

Dreger et al. (Ind. Eng. Chem. 36 (1944) 610) prepared secondary alcohol sulfates having 11 to 19 carbons. Some of these were “sym-sec-alcohol sulfates” in which the sulfate group was bonded to a central carbon (e.g., sodium 7-tridecyl sulfate or sodium 8-pentadecyl sulfate). Detergency of these compositions was evaluated in hot (43° C.) water. The authors concluded that “when other factors are the same, the nearer the polar group is to the end of a straight-chain alcohol sulfate, the better the detergency.” Cold-water performance was not evaluated.

Similarly, Finger et al. (J. Am. Oil Chem. Soc. 44 (1967) 525) studied the effect of alcohol structure and molecular weight on properties of the corresponding sulfates and ethoxyate sulfates. The authors included sodium 7-tridecyl sulfate and sodium 7-pentadecyl sulfate in their study. They concluded that moving the polar group away from the terminal position generally decreases cotton detergency and foam performance.

Mid-chain surfactants having functional groups other than sulfates have been described. U.S. Pat. Appl. Publ. No. 2007/0111924, for instance, teaches liquid laundry detergents comprising a sulfate or sulfonate component and a mid-chain amine oxide. Mid-chain sulfonates, sometimes referred to as “double tailed” sulfonates, are also known (see, e.g., R. Granet et al., Colloids Surf. 33 (1988) 321; 49 (1990) 199); the performance of these materials in laundry applications has not been reported.

Internal olefin sulfonates are well known. Although they are useful for enhanced oil recovery (see, e.g., U.S. Pat. Appl. No. 2010/0282467), they have also been suggested for use in detergent compositions, including laundry detergents (see U.S. Pat. No. 5,078,916). These are prepared by sulfonating mixtures of internal olefins. Commercially available internal olefins, including the Neodene® products of Shell, are generated by isomerizing alpha olefins in the presence of a catalyst that also scatters the location of the carbon-carbon double bond. Consequently, sulfonates made from the internal olefins (including the commercial Enordet® products from Shell) do not have a well-defined location for the polar group.

Surfactants in which the polar group is separated from the principal alkyl chain by an alkylene bridge are known. Some methylene-bridged surfactants of this type are derived from “Guerbet” alcohols. Guerbet alcohols can be made by dimerizing linear or branched aliphatic alcohols using a basic catalyst using chemistry first discovered in the 19th century. The alcohols, which have a —CH₂— bridge to the hydroxyl group near the center of the alkyl chain, can be converted to alkoxylates, sulfates, and ether sulfates (see, e.g., Varadaraj et al., J. Phys. Chem. 95 (1991), 1671, 1677, 1679, and 1682). The Guerbet derivatives have not apparently been shown to have any particular advantage for cold-water cleaning.

Surprisingly few references describe surfactants that demonstrate improved cleaning using cold water (i.e., less than 30° C.). U.S. Pat. No. 6,222,077 teaches dimerized alcohol compositions and biodegradable surfactants made from them having cold water detergency. A few examples are provided to show improved cold water detergency on an oily (multisebum) soil when compared with a sulfated Neodol® C₁₄-C₁₅alcohol. Made by dimerizing internal or alpha olefins (preferably internal olefins) in multiple stages followed by hydroformylation, these surfactants are difficult to characterize. As shown in Examples 1-3 of Table 1 of the '077 patent, NMR characterization shows that a single dimerized alcohol product typically has multiple components and a wide distribution of branch types (methyl, ethyl, propyl, butyl, and higher) and various attachment points on the chain for the branches. A high degree of methyl branching (14-20%) and ethyl branching (13-16%) is also evident.

PCT Int. Appl. No. WO 01/14507 describes laundry detergents that combine a C₁₆Guerbet alcohol sulfate and an alcohol ethoxylate. Compared with similar fully formulated detergents that utilize a linear C₁₆alcohol sulfate, the detergent containing the Guerbet alcohol sulfate provides better cleaning in hot (60° C.) or warm (40° C.) water. Laundering with cold (<30° C.) water is not disclosed or suggested.

PCT Int. Appl. No. WO 2013/181083 teaches laundry detergent compositions made by dimerizing even-numbered alpha-olefins to produce vinylidenes, hydroformylation of the vinylidenes to give alcohols mixtures, and sulfation of the alcohols. Hydroformylation is performed in a manner effective to provide alcohol mixtures in which methyl-branched products predominate. According to the inventors, methyl branching on even-numbered carbons on the alkyl chain is believed to contribute to rapid biodegradation in sulfate surfactants made from the alcohols. When compared with similar sulfates having random branching on the chain, those with branching on even-numbered carbons had similar cleaning ability at 20° C. but improved biodegradability.

Improved detergents are always in need, especially laundry detergents that perform well in cold water. Of particular interest are detergents that can tackle greasy dirt such as bacon grease or beef tallow, because these stains solidify and adhere strongly to common textile fibers. Ideally, the kind of cleaning performance on greasy dirt that consumers are used to enjoying when using hot water could be realized even with cold water.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a detergent that is useful for cold-water cleaning. The detergent comprises a mid-chain headgroup surfactant. The surfactant has a saturated or unsaturated, linear or branched C₁₄-C₃₀alkyl chain. In addition, the surfactant has a polar group (or “headgroup”) bonded to a central zone carbon of the C₁₄-C₃₀alkyl chain. Preferred mid-chain headgroup surfactants are alcohol sulfates, alcohol ethoxylates, ether sulfates, sulfonates, aryl sulfonates, alcohol phosphates, amine oxides, quaterniums, betaines, and sulfobetaines.

In other aspects, the invention relates to mid-chain headgroup surfactants having a polar group bonded to a central zone carbon of the C₁₄-C₃₀alkyl chain described above. The alkyl chain may be obtained from olefin metathesis. It may also be obtained from a fermentation process using a bacterium, algae or yeast-based microbe.

A variety of laundry detergent formulations comprising the mid-chain headgroup surfactants are also included.

In another aspect, the invention relates to a cold-water cleaning method. The method comprises laundering a soiled textile article in water having a temperature less than 30° C. in the presence of a detergent to produce a cleaned textile article. The detergent comprises a mid-chain, alkylene-bridged headgroup surfactant. This surfactant has a saturated or unsaturated, linear or branched C₁₂-C₁₈alkyl chain, a polar group, and a C₁-C₂alkylene group bonded to the polar group and a central zone carbon of the C₁₂-C₁₈alkyl chain. The surfactant has, excluding the polar group, a total of 14 to 19 carbons. Preferred alkylene-bridged surfactants are alcohol sulfates, alcohol alkoxylates, ether sulfates, sulfonates, aryl sulfonates, alcohol phosphates, amine oxides, quaterniums, betaines, and sulfobetaines.

The invention includes a method which comprises liquefying a greasy soil in water at a temperature less than 30° C. using the alkylene-bridged surfactants.

We surprisingly found that surfactants having a long enough alkyl chain and a centrally located polar group provide outstanding performance in removing greasy stains such as bacon grease, butter, cooked beef fat, or beef tallow from soiled articles. Detergents formulated with the surfactants outperform control cold-water detergents by a wide margin. We also found that detergents formulated with alkylene-bridged surfactants effectively liquefy greasy soils at low temperature and provide outstanding cold-water performance in removing these greasy stains from soiled articles.

DETAILED DESCRIPTION OF THE INVENTION

Section I describes mid-chain headgroup surfactants and their use in detergents for cold-water cleaning. Section II describes mid-chain, alkylene-bridged headgroup surfactants and their use in detergents for cold-water cleaning.

I. Mid-Chain Headgroup Surfactants

In one aspect, the invention relates to detergents useful for cold-water cleaning. The detergents comprise a mid-chain headgroup surfactant. The mid-chain headgroup surfactant has a saturated or unsaturated, linear or branched C₁₄-C₃₀alkyl chain and a polar group bonded to a central zone carbon of the C₁₄-C₃₀alkyl chain.

“Cold water” means water having a temperature less than 30° C., preferably from 5° C. to 28° C., more preferably 8° C. to 25° C. Depending on climate, sourced water will have a temperature in this range without requiring added heat.

“Mid-chain headgroup” surfactant means a surfactant in which the polar group is located at or near the center of the longest continuous alkyl chain.

The “central carbon” of the C₁₄-C₃₀alkyl chain is identified by: (1) finding the longest continuous alkyl chain; (2) counting the number of carbons in that chain; (3) dividing the number of carbons in the longest chain by 2. When the longest continuous carbon chain has an even number of carbons, the central carbon is found by counting from either chain end the result in (3). In this case, there will be two possible attachment sites. When the longest continuous carbon chain has an odd number of carbons, the result in (3) is rounded up to the next highest integer value, and the central carbon is found by counting from either chain end that rounded-up result. There will be only one possible attachment site.

For example, consider sodium 9-octadecyl sulfate. The longest continuous carbon chain has 18 carbons. Dividing 18 by 2 gives 9. Counting 9 carbons from either end and attaching the polar group gives the same result from either end because of the lack of any branching in the C₁₈chain.

As another example, consider sodium 2-methyl-8-pentadecyl sulfate. The longest continuous carbon chain has 15 carbons. Dividing 15 by 2 gives 7.5. We round 7.5 up to 8, then count 8 carbons from either end and attach the polar group.

By “central zone carbon,” we mean a “central carbon” as defined above, or a carbon in close proximity to the central carbon. When the longest continuous alkyl chain has an even number of carbons, the two central carbons and any carbon in the α- or β-position with respect to either central carbon are within the “central zone.” When the longest continuous alkyl chain has an odd number of carbons, the central carbon and any carbon in the α-, β-, or γ-position with respect to the central carbon are within the “central zone.”

Another way to identify the central zone carbons is as follows. Let N=the number of carbons in the longest continuous alkyl chain. N has a value from 14 to 30. When N is even, the central zone carbons are found by counting N/2, (N/2)−1, or (N/2)−2 carbons from either end of the chain. When N is odd, the central zone carbons are found by counting (N+1)/2, [(N+1)/2]−1, [(N+1)/2]−2, or [(N+1)/2]−3 carbons from either end of the chain.

For example, when N=25, the central zone carbons will be found by counting 13, 12, 11, or 10 carbons from either end of the chain. When N=18, the central zone carbons will be found by counting 9, 8, or 7 carbons from either end of the chain.

Based on the above considerations, detergents considered to be within the invention will comprise a mid-chain headgroup surfactant having one or more of the following configurations: 14-7, 14-6, 14-5, 15-8, 15-7, 15-6, 15-5, 16-8, 16-7, 16-6, 17-9, 17-8, 17-7, 17-6, 18-9, 18-8, 18-7, 19-10, 19-9, 19-8, 19-7, 20-10, 20-9, 20-8, 21-11, 21-10, 21-9, 21-8, 22-11, 22-10, 22-9, 23-12, 23-11, 23-10, 23-9, 24-12, 24-11, 24-10, 25-13, 25-12, 25-11, 25-10, 26-13, 26-12, 26-11, 27-14, 27-13, 27-12, 27-11, 28-14, 28-13, 28-12, 29-15, 29-14, 29-13, 29-12, 30-15, 30-14, and 30-13 where the first number is N, the number of carbons in the longest continuous alkyl chain, and the second number is the location of the polar group in terms of the number of carbons away from one end of the alkyl chain.

The mid-chain headgroup surfactant has a saturated or unsaturated, linear or branched C₁₄-C₃₀alkyl chain, preferably a C₁₄-C₂₀alkyl chain, even more preferably a C₁₄-C₁₈alkyl chain.

In mid-chain headgroup surfactants for which the longest continuous alkyl chain has an even number of carbons, the polar group is preferably attached to one of the two central carbons or a carbon in the α-position with respect to either central carbon. More preferably, the polar group is attached to one of the two central carbons.

In mid-chain headgroup surfactants for which the longest continuous alkyl chain has an odd number of carbons, the polar group is preferably attached to the central carbon or a carbon in the α- or β-position with respect to the central carbon. More preferably, the polar group is attached to the central carbon or a carbon in the α-position with respect to the central carbon. Most preferably, the polar group is attached to the central carbon.

Preferably, the detergent comprises water in addition to the mid-chain headgroup surfactant. The amount of water present may vary over a wide range and will normally depend on the intended application, the form in which the detergent is delivered, the desired actives level, and other factors. In actual use, the detergents will normally be diluted with a small, large, or very large proportion of water, depending on the equipment available for washing. Generally, the amount of water used will be effective to give 0.001 to 5 wt. % of active surfactant in the wash.

Preferred detergents comprise 1 to 70 wt. %, more preferably 1 to 30 wt. % or 2 to 15 wt. %, of the mid-chain headgroup surfactant (based on 100% actives).

A variety of polar groups are considered suitable for use, as the location on the chain appears to be more important than the nature of the polar group. Thus, suitable mid-chain headgroup surfactants include alcohol sulfates, alcohol ethoxylates, ether sulfates, sulfonates, aryl sulfonates, alcohol phosphates, amine oxides, quaterniums, betaines, sulfobetaines, and the like, and their mixtures. Alcohol sulfates, ether sulfates, and sulfonates are particularly preferred mid-chain headgroup surfactants.

The alcohol sulfates are conveniently made by reacting the corresponding alcohol with a sulfating agent according to known methods (see, e.g., U.S. Pat. No. 3,544,613, the teachings of which are incorporated herein by reference). Sulfamic acid is a convenient reagent that sulfates the hydroxyl group without disturbing any unsaturation present in the alkyl chain. Thus, warming the alcohol with sulfamic acid optionally in the presence of urea or another proton acceptor conveniently provides the desired alkyl ammonium sulfate. The ammonium sulfate is easily converted to an alkali metal sulfate by reaction with an alkali metal hydroxide (e.g., sodium hydroxide) or other ion-exchange reagents (see preparation of sodium 9-octadecyl sulfate, below) Other suitable sulfating agents include sulfur trioxide, oleum, and chlorosulfonic acid may be used.

The alcohol precursors to the sulfates can be purchased or synthesized. When the mid-chain alcohol is not commercially available, it usually can be prepared from an aldehyde, an alkyl halide, and magnesium using a conventional Grignard reaction. Other methods exist, including forming an internal olefin via metathesis, followed by reaction of the internal olefin under cold conditions with sulfuric acid, followed by either cold neutralization of the resulting sulfate, or hydrolysis of the sulfate ester with warm water.

When an alcohol ethoxylate is desired, the alcohol precursor is reacted with ethylene oxide, usually in the presence of a base, to add a desired average number of oxyethylene units. Typically, the number of oxyethylene units ranges from 0.5 to 100, preferably from 1 to 30, more preferably from 1 to 10.

When an ether sulfate is desired, the alcohol precursor is first alkoxylated by reacting it with ethylene oxide, propylene oxide, or a combination thereof to produce an alkoxylate. Alkoxylations are usually catalyzed by a base (e.g., KOH), but other catalysts such as double metal cyanide complexes (see, e.g., U.S. Pat. No. 5,482,908) can also be used. The oxyalkylene units can be incorporated randomly or in blocks. Sulfation of the alcohol alkoxylate (usually an alcohol ethoxylate) gives the desired ether sulfate.

Suitable fatty alcohol precursors to the mid-chain sulfates or ether sulfates include, for example, 7-tetradecanol, 6-tetradecanol, 5-tetradecanol, 8-pentadecanol, 7-pentadecanol, 6-pentadecanol, 5-pentadecanol, 8-hexadecanol, 7-hexadecanol, 6-hexadecanol, 9-septadecanol, 8-septadecanol, 7-septadecanol, 6-septadecanol, 9-octadecanol, 8-octadecanol, 7-octadecanol, 10-nonadecanol, 9-nonadecanol, 8-nonadecanol, 7-nonadecanol, 10-eicosanol, 9-eicosanol, 8-eicosanol, 11-heneicosanol, 10-heneicosanol, 9-heneicosanol, 8-heneicosanol, 11-docosanol, 10-docosanol, 9-dococanol, 12-tricosanol, 11-tricosanol, 10-tricosanol, 9-tricosanol, 12-tetracosanol, 11-tetracosanol, 10-tetracosanol, 9-tetracosanol, 13-pentacosanol, 12-pentacosanol, 11-pentacosanol, 10-pentacosanol, 13-hexacosanol, 12-hexacosanol, 11-hexacosanol, 14-heptacosanol, 13-heptacosanol, 12-heptacosanol, 11-heptacosanol, 14-octacosanol, 13-octacosanol, 12-octacosanol, 15-nonacosanol, 14-nonacosanol, 13-nonacosanol, 12-nonacosanol, 15-triacontanol, 14-triacontanol, 13-triacontanol, and the like, and mixtures thereof. 9-Octadecanol and 8-hexadecanol are particularly preferred.

Mid-chain sulfonates can be made by reacting an internal olefin with a sulfonating agent. Sulfonation is performed using well-known methods, including reacting the olefin with sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid, or other known sulfonating agents. Chlorosulfonic acid is a preferred sulfonating agent. The sultones that are the immediate products of reacting olefins with SO₃, chlorosulfonic acid, and the like may be subsequently subjected to hydrolysis and neutralization with aqueous caustic to afford mixtures of alkene sulfonates and hydroxyalkane sulfonates. Suitable methods for sulfonating olefins are described in U.S. Pat. Nos. 3,169,142; 4,148,821; and U.S. Pat. Appl. Publ. No. 2010/0282467, the teachings of which are incorporated herein by reference.

Suitable mid-chain sulfonates can be made by sulfonating internal olefins. Preferred internal olefins include, for example, 7-tetradecene, 6-tetradecene, 5-tetradecene, 8-pentadecene, 7-pentadecene, 6-pentadecene, 5-pentadecene, 8-hexadecene, 7-hexadecene, 6-hexadecene, 9-septadecene, 8-septadecene, 7-septadecene, 6-septadecene, 9-octadecene, 8-octadecene, 7-octadecene, 10-nonadecene, 9-nonadecene, 8-nonadecene, 7-nonadecene, 10-eicosene, 9-eicosene, 8-eicosene, 11-heneicosene, 10-heneicosene, 9-heneicosene, 8-heneicosene, 11-docosene, 10-docosene, 9-docosene, 12-tricosene, 11-tricosene, 10-tricosene, 9-tricosene, 12-tetracosene, 11-tetracosene, 10-tetracosene, 13-pentacosene, 12-pentacosene, 11-pentacosene, 10-pentacosene, 13-hexacosene, 12-hexacosene, 11-hexacosene, 14-heptacosene, 13-heptacosene, 12-heptacosene, 11-heptacosene, 14-octacosene, 13-octacosene, 12-octacosene, 15-nonacosene, 14-nonacosene, 13-nonacosene, 12-nonacosene, 15-triacontene, 14-triacontene, 13-triacontene, and mixtures thereof.

Internal olefin precursors to the mid-chain sulfonates can be prepared by olefin metathesis (and subsequent fractionation), alcohol dehydration, pyrolysis, elimination reactions, the Wittig reaction (see, e.g., Angew. Chem., Int. Ed. Engl. 4 (1965) 830; Tetrahedron Lett. 26 (1985) 307; and U.S. Pat. No. 4,642,364), and other synthetic methods known to those skilled in the art. For more examples of suitable methods, see I. Harrison and S. Harrison, Compendium of Organic Synthetic Methods, Vol. I (1971) (Wiley) and references cited therein.

Mid-chain arylsulfonates can be made by alkylating arenes such as benzene, toluene, xylenes, or the like, with internal olefins, followed by sulfonation of the aromatic ring and neutralization.

The alcohol precursors to mid-chain headgroup surfactants mentioned above can be converted to the corresponding amines by an amination process. In some cases, it may be more desirable to make the amines through an intermediate such as a halide or other compound having a good leaving group.

The mid-chain amine oxides and quaterniums are conveniently available from the corresponding tertiary amines by oxidation or quaternization. The mid-chain betaines and sulfobetaines are conveniently available from the corresponding primary amines by reaction with, e.g., sodium monochloroacetate (betaines) or sodium metabisulfite and epichlorohydrin in the presence of base (sulfobetaines). For examples of how to prepare quaterniums, betaines, and sulfobetaines, see PCT Int. Publ. No. WO2012/061098, the teachings of which are incorporated herein by reference.

The saturated or unsaturated, linear or branched C₁₄-C₃₀alkyl chain may be obtained from olefin metathesis, particularly a tungsten, molybdenum, or ruthenium-catalyzed olefin metathesis. Generally, this will provide an internal olefin, which provides the desired starting material for making the mid-chain sulfonate.

The C₁₄-C₃₀alkyl chain may also be obtained from a fermentation process using a bacterium, algae or yeast-based microbe, which may or may not be genetically modified (see, e.g., WO 2011/13980, WO2011/056183, and U.S. Pat. Nos. 7,018,815, 7,935,515, 8,216,815, 8,278,090, 8,268,599, and 8,323,924).

In certain preferred aspects, the detergent compositions further comprise a nonionic surfactant, which is preferably a fatty alcohol ethoxylate.

In other preferred aspects, the detergents further comprise an anionic surfactant, preferably one selected from linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, fatty alcohol sulfates, and mixtures thereof.

In another preferred aspect, the detergent is in the form of a liquid, powder, paste, granule, tablet, or molded solid, or a water-soluble sheet, sachet, capsule, or pod.

In another preferred aspect, the detergent further comprises water, a fatty alcohol ethoxylate, and an anionic surfactant selected from linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, and fatty alcohol sulfates.

In another preferred aspect, the detergent comprises 1 to 70 wt. %, preferably 5 to 15 wt. %, of a fatty alcohol ethoxylate, 1 to 70 wt. %, preferably 1 to 20 wt. %, of the mid-chain headgroup surfactant, and 1 to 70 wt. %, preferably 5 to 15 wt. %, of an anionic surfactant selected from linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, and fatty alcohol sulfates.

In another aspect, the invention relates to mid-chain headgroup surfactants. The surfactants comprise a saturated or unsaturated, linear or branched C₁₄-C₃₀alkyl chain, and a polar group bonded to a central zone carbon of the C₁₄-C₃₀alkyl chain. The alkyl chain may be obtained from olefin metathesis, preferably from a tungsten, molybdenum, or ruthenium-catalyzed olefin metathesis.

In another aspect, the alkyl chain is obtained via a fermentation process using a bacterium, algae or yeast-based microbe that may or may not be genetically modified.

In one aspect, the invention relates to a composition comprising a mid-chain headgroup surfactant of the invention and water, a solvent, a hydrotrope, an auxiliary surfactant, or mixtures thereof. The solvent and/or auxiliary surfactant and hydrotrope usually help to compatibilize a mixture of water and the mid-chain headgroup surfactant. An “incompatible” mixture of water and a mid-chain headgroup surfactant (absent a solvent and/or auxiliary) is opaque at temperatures between about 15° C. and 25° C. This product form is difficult to ship and difficult to formulate into commercial detergent formulations. In contrast, a “compatible” mixture of water and mid-chain headgroup surfactant is transparent or translucent, and it flows readily when poured or pumped at temperatures within the range of about 15° C. to 25° C. This product form provides ease of handling, shipping, and formulating from a commercial perspective.

Suitable solvents include, for example, isopropanol, ethanol, 1-butanol, ethylene glycol n-butyl ether, the Dowanol® series of solvents, propylene glycol, butylene glycol, propylene carbonate, ethylene carbonate, solketal, and the like. Preferably, the composition should comprise less than 25 wt. %, more preferably less than 15 wt. %, and most preferably less than 10 wt. % of the solvent (based on the combined amounts of mid-chain headgroup surfactant, solvent, hydrotrope, and any auxiliary surfactant).

Hydrotropes have the ability to increase the water solubility of organic compounds that are normally only slightly soluble in water. Suitable hydrotropes for formulating detergents for cold water cleaning are preferably short-chain surfactants that help to solubilize other surfactants. Preferred hydrotropes for use herein include, for example, aryl sulfonates (e.g., cumene sulfonates, xylene sulfonates), short-chain alkyl carboxylates, sulfosuccinates, urea, short-chain alkyl sulfates, short-chain alkyl ether sulfates, and the like, and combinations thereof. When a hydrotrope is present, the composition preferably comprises less than 25 wt. %, more preferably less than 10 wt. % of the hydrotrope (based on the combined amounts of mid-chain headgroup surfactant, solvent, hydrotrope, and any auxiliary surfactant).

Suitable auxiliary surfactants include, for example, N,N-diethanol oleamide, N,N-diethanol C₈to C₁₈saturated or unsaturated fatty amides, ethoxylated fatty alcohols, alkyl polyglucosides, alkyl amine oxides, N,N-dialkyl fatty amides, oxides of N,N-dialkyl aminopropyl fatty amides, N,N-dialkyl aminopropyl fatty amides, alkyl betaines, linear C₁₂-C₁₈sulfates or sulfonates, alkyl sulfobetaines, alkylene oxide block copolymers of fatty alcohols, alkylene oxide block copolymers, and the like. Preferably, the composition should comprise less than 25 wt. %, more preferably less than 15 wt. %, and most preferably less than 10 wt. % of the auxiliary surfactant (based on the combined amounts of mid-chain headgroup surfactant, auxiliary surfactant, and any solvent).

The inventive detergent compositions provide improved cold-water cleaning performance. It is common in the field to launder stained fabric swatches under carefully controlled conditions to measure a stain removal index (SRI). Details of the procedure appear in the experimental section below. The inventive compositions can provide a stain removal index improvement of at least 0.5 units, preferably at least 1.0 unit, and more preferably at least 2.0 units at the same wash temperature less than 30° C. on at least one greasy soil when compared with the stain removal index provided by similar compositions in which the detergent comprises a primary surfactant other than the mid-chain headgroup surfactant. Greasy soils include, for example, bacon grease, beef tallow, butter, cooked beef fat, solid oils, vegetable waxes, petroleum waxes, and the like. On the SRI scale, differences of 0.5 units are distinguishable with the naked eye. Herein, we compare performance of the mid-chain headgroup surfactant with primary surfactants currently used in cold-water detergents. In particular, the comparative surfactants are a sodium C₁₂-C₁₄alcohol ethoxylate sulfate (Na AES) or a sodium linear alkylbenzene sulfonate (Na LAS) as shown in the examples below.

In other preferred aspects, the invention relates to particular laundry detergent formulations comprising the inventive detergents.

One such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention and has a pH within the range of 7 to 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

a sufficient amount of at least three enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, and derivatives thereof.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention and has a pH within the range of 7 to 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and a sufficient amount of one or two enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, and derivatives thereof.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention, has a pH within the range of 7 to 10, and is substantially free of enzymes. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant; and

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention and has a pH within the range of 7 to 12. This detergent further comprises:

1 to 70 wt. %, preferably 4 to 50 wt. %, of at least one C₁₆α-methyl ester sulfonate; and

0 to 70 wt. %, preferably 0 to 25 wt. %, of cocamide diethanolamine.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention and has a pH greater than 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

0.1 to 5 wt. % of metasilicate.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent of the invention and has a pH greater than 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

0.1 to 20 wt. % of sodium carbonate.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent of the invention. This detergent further comprises:

2 to 70 wt. %, preferably 2 to 40 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 32 wt. %, of at least one alcohol ether sulfate;

0 to 65 wt. %, preferably 0 to 25 wt. %, of at least one C₁₆α-methyl ester sulfonate;

0 to 6 wt. % of lauryl dimethylamine oxide;

0 to 6 wt. % of C₁₂EO₃;

0 to 10 wt. % of coconut fatty acid;

0 to 3 wt. % of borax pentahydrate;

0 to 6 wt. % of propylene glycol;

0 to 10 wt. % of sodium citrate;

0 to 6 wt. % of triethanolamine;

0 to 6 wt. % of monoethanolamine;

0 to 1 wt. % of at least one fluorescent whitening agent;

0 to 1.5 wt. % of at least one anti-redeposition agent;

0 to 2 wt. % of at least one thickener;

0 to 2 wt. % of at least one thinner;

0 to 2 wt. % of at least one protease;

0 to 2 wt. % of at least one amylase; and

0 to 2 wt. % of at least one cellulase.

Yet another such laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent of the invention. This detergent further comprises:

2 to 70 wt. %, preferably 2 to 40 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 32 wt. %, of at least one alcohol ether sulfate;

0 to 6 wt. % of lauryl dimethylamine oxide;

0 to 6 wt. % of C₁₂EO₃;

0 to 10 wt. % of coconut fatty acid;

0 to 10 wt. % of sodium metasilicate;

0 to 10 wt. % of sodium carbonate;

0 to 1 wt. % of at least one fluorescent whitening agent;

0 to 1.5 wt. % of at least one anti-redeposition agent;

0 to 2 wt. % of at least one thickener; and

0 to 2 wt. % of at least one thinner.

Another “green” laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent of the invention. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 30 wt. %, of at least one C₁₆methyl ester sulfonate;

0 to 70 wt. %, preferably 0 to 30 wt. %, of at least one C₁₂methyl ester sulfonate;

0 to 70 wt. %, preferably 0 to 30 wt. %, of sodium lauryl sulfate;

0 to 30 wt. % of sodium stearoyl lactylate;

0 to 30 wt. % of sodium lauroyl lactate;

0 to 70 wt. %, preferably 0 to 60 wt. %, of alkyl polyglucoside;

0 to 70 wt. %, preferably 0 to 60 wt. %, of polyglycerol monoalkylate;

0 to 30 wt. % of lauryl lactyl lactate;

0 to 30 wt. % of saponin;

0 to 30 wt. % of rhamnolipid;

0 to 30 wt. % of sphingolipid;

0 to 30 wt. % of glycolipid;

0 to 30 wt. % of at least one abietic acid derivative; and

0 to 30 wt. % of at least one polypeptide.

In one aspect, the inventive mid-chain headgroup surfactant is used in a laundry pre-spotter composition. In this application, greasy or oily soils on the garments or textile fabrics are contacted directly with the pre-spotter in advance of laundering either manually or by machine. Preferably, the fabric or garment is treated for 5-30 minutes. The amount of active mid-chain headgroup surfactant in the pre-spotter composition is preferably 0.5 to 50 wt. %, more preferably 1 to 30 wt. %, and most preferably 5 to 20 wt. %. Treated fabric is machine laundered as usual, preferably at a temperature within the range of 5° C. and 30° C., more preferably 10° C. to 20° C., most preferably 12° C. to 18° C.

In another aspect, the inventive mid-chain headgroup surfactant is used in a pre-soaker composition for manual or machine washing.

When used for manual washing, the pre-soaker composition is combined with cold water in a washing tub or other container. The amount of active mid-chain headgroup surfactant in the pre-soaker composition is preferably 0.5 to 100 wt. %, more preferably 1 to 80 wt. %, and most preferably 5 to 50 wt. %. Garments or textile fabrics are preferably saturated with pre-soaker in the tub, allowed to soak for 15-30 minutes, and laundered as usual.

When used for machine washing, the pre-soaker composition is preferably added to a machine containing water at a temperature within the range of 5° C. and 30° C., more preferably 10° C. to 20° C., most preferably 12° C. to 18° C. The amount of active mid-chain headgroup surfactant in the pre-soaker composition is preferably 0.5 to 100 wt. %, more preferably 1 to 80 wt. %, and most preferably 5 to 50 wt. %. Garments/textile fabrics are added to the machine, allowed to soak (usually with a pre-soak cycle selected on the machine) for 5-10 minutes, and then laundered as usual.

In another aspect, the mid-chain branched headgroup surfactant is used as an additive for a laundry product or formulation. In such applications, the surfactant helps to improve or boost the grease removal or grease cutting performance of the laundry product or formulation. Preferably, the amount of mid-chain branched headgroup surfactant actives used will be within the range of 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 3 to 5 wt. %. The laundry product or formulation and the mid-chain branched headgroup surfactant are preferably mixed until a homogeneous composition is obtained.

In yet another aspect, the mid-chain branched headgroup surfactant is used as a surfactant additive. In such applications, the resulting modified surfactant will have improved grease removal or grease cutting properties. Preferably, the amount of mid-chain branched headgroup surfactant actives used will be within the range of 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 3 to 5 wt. %. The resulting modified surfactant will help to achieve improved grease cutting/removal in commercial products. Such products may be used at a temperature within the range of 5° C. and 30° C., preferably 10° C. to 20° C., and more preferably 12° C. to 18° C.

II. Mid-Chain Alkylene-Bridged Headgroup Surfactants

In another aspect, the invention relates to a cold-water cleaning method. The method comprises laundering one or more textile articles in water having a temperature less than 30° C. in the presence of a detergent. The detergent comprises a mid-chain, alkylene-bridged headgroup surfactant (also referred to herein as the “alkylene-bridged surfactant”). This surfactant has (a) a saturated or unsaturated, linear or branched C₁₂-C₁₈alkyl chain; (b) a polar group; and (c) a C₁-C₂alkylene group bonded to the polar group and a central zone carbon of the C₁₂-C₁₈alkyl chain. Excluding the polar group, the surfactant has a total of 14 to 19 carbons, preferably 15 to 19 carbons, more preferably 16 to 18 carbons.

In this aspect of the invention, “cold water” means water having a temperature less than 30° C., preferably from 5° C. to 28° C., more preferably 8° C. to 25° C. Depending on climate, sourced water will have a temperature in this range without requiring added heat.

“Mid-chain alkylene-bridged headgroup surfactant” means a surfactant in which the polar group is bonded to a C₁-C₂alkylene bridge, and this bridge is bonded to a carbon located at or near the center of the longest continuous alkyl chain, excluding the C₁-C₂alkylene group.

The “central carbon” of the C₁₂-C₁₈alkyl chain is identified by: (1) finding the longest continuous alkyl chain excluding the C₁-C₂alkylene group; (2) counting the number of carbons in that chain; (3) dividing the number of carbons in that longest chain by 2. When the longest continuous carbon chain (excluding the C₁-C₂alkylene group) has an even number of carbons, the central carbon is found by counting from either chain end the result in (3). In this case, there will be two possible attachment sites for the alkylene bridge. When the longest continuous carbon chain (excluding the C₁-C₂alkylene group) has an odd number of carbons, the result in (3) is rounded up to the next highest integer value, and the central carbon is found by counting from either chain end that rounded-up result. There will be only one possible attachment site.

For example, consider sodium 2-hexyl-1-undecyl sulfate. The longest continuous carbon chain (excluding the —CH₂— bridge) has 16 carbons. Dividing 16 by 2 gives 8. We count 8 carbons from either end to locate either of two central carbons.

As another example, consider sodium 2-octyl-1-decyl sulfate. The longest continuous carbon chain (excluding the —CH₂— bridge) has 17 carbons. Dividing 17 by 2 gives 8.5. We round up 8.5 to 9. Counting 9 carbons from either end provides the location of the lone central carbon.

By “central zone carbon,” we mean a “central carbon” as defined above, or a carbon in close proximity to the central carbon. When the longest continuous alkyl chain (excluding the C₁-C₂alkylene group) has an even number of carbons, the two central carbons and any carbon in the α- or β-position with respect to either central carbon are within the “central zone.” When the longest continuous alkyl chain (excluding the C₁-C₂alkylene group) has an odd number of carbons, the central carbon and any carbon in the α-, β-, or γ-position with respect to the central carbon are within the “central zone.” Another way to identify the central zone carbons is as follows. Let N=the number of carbons in the longest continuous alkyl chain (excluding the C₁-C₂alkylene group). N has a value from 12 to 18. When N is even, the central zone carbons are found by counting N/2, (N/2)−1, or (N/2)−2 carbons from either end of the chain. When N is odd, the central zone carbons are found by counting (N+1)/2, [(N+1)/2]−1, [(N+1)/2]−2, or [(N+1)/2]−3 carbons from either end of the chain.

For example, when N=15, the central zone carbons will be found by counting 8, 7, 6, or 5 carbons from either end of the chain. When N=18, the central zone carbons will be found by counting 9, 8, or 7 carbons from either end of the chain.

Based on the above considerations, detergents considered to be within the invention will comprise an alkylene-bridged surfactant having one or more of the following configurations: 12-6, 12-5, 12-4, 13-7, 13-6, 13-5, 13-4, 14-7, 14-6, 14-5, 15-8, 15-7, 15-6, 15-5, 16-8, 16-7, 16-6, 17-9, 17-8, 17-7, 17-6, 18-9, 18-8, and 18-7, where the first number is N, the number of carbons in the longest continuous alkyl chain (excluding the C₁-C₂alkylene group), and the second number is the location of the alkylene-bridged polar group in terms of the number of carbons away from one end of the alkyl chain.

In alkylene-bridged surfactants for which the longest continuous alkyl chain (excluding the C₁-C₂alkylene group) has an even number of carbons, the alkylene bridge is preferably attached to one of the two central carbons or a carbon in the α-position with respect to either central carbon. More preferably, the alkylene bridge is attached to one of the two central carbons.

In alkylene-bridged surfactants for which the longest continuous alkyl chain (excluding the C₁-C₂alkylene group) has an odd number of carbons, the alkylene bridge is preferably attached to the central carbon or a carbon in the α- or β-position with respect to the central carbon. More preferably, the alkylene bridge is attached to the central carbon or a carbon in the α-position with respect to the central carbon. Most preferably, the alkylene bridge is attached to the central carbon.

Preferably, the detergent comprises water in addition to the alkylene-bridged surfactant. The amount of water present may vary over a wide range and will normally depend on the intended application, the form in which the detergent is delivered, the desired actives level, and other factors. In actual use, the detergents will normally be diluted with a small, large, or very large proportion of water, depending on the equipment available for washing. Generally, the amount of water used will be effective to give 0.001 to 5 wt. % of active surfactant in the wash.

Preferred detergents comprise 1 to 70 wt. %, more preferably 1 to 30 wt. % or 2 to 15 wt. %, of the alkylene-bridged surfactant (based on 100% actives).

In addition to the mid-chain, alkylene-bridged surfactant, the detergents used in the cold-water cleaning method may comprise some proportion of alkyl-branched surfactant components. Preferably, the detergents comprise at most only a minor proportion of alkyl-branched components. In one aspect, the mid-chain, alkylene-bridged surfactant has a minor proportion of methyl or ethyl branches on the longest continuous alkyl chain or on the alkylene bridge. In a preferred aspect, at least 50 mole %, more preferably at least 70 mole %, of the alkylene-bridged surfactant is essentially free of methyl or ethyl branching.

A variety of polar groups are considered suitable for use, as the location on the chain appears to be more important than the nature of the polar group. Thus, suitable alkylene-bridged surfactants include alcohol sulfates, alcohol alkoxylates, ether sulfates, sulfonates, aryl sulfonates, alcohol phosphates, amine oxides, quaterniums, betaines, sulfobetaines, and the like, and their mixtures. Alcohol sulfates, ether sulfates, and sulfonates are particularly preferred.

Alcohol precursors to the sulfates and ether sulfates can be purchased or synthesized. Suitable Guerbet alcohols, which have a —CH₂—“bridge” to the hydroxyl group, are commercially available from Sasol (ISOFOL® alcohols), BASF (e.g., Eutanol® alcohols), Lubrizol, and other suppliers. Commercially available examples include 2-butyl-1-decanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-hexyl-1-dodecanol, and the like. Suitable Guerbet alcohols can also be synthesized. In the classical synthetic approach, the Guerbet alcohol is made by reacting two moles of an aliphatic alcohol at elevated temperature in the presence of a suitable catalyst to induce oxidation of the alcohol to an aldehyde, aldol condensation, dehydration, and hydrogenation to provide the resulting Guerbet product. Suitable catalysts include, among others, nickel, lead salts (see, e.g., U.S. Pat. No. 3,119,880), oxides of copper, lead, zinc, and other metals (U.S. Pat. No. 3,558,716), or palladium and silver compounds (see, e.g., U.S. Pat. No. 3,979,466 or 3,864,407). The reaction of two moles of 1-octanol to give 2-hexyl-1-decanol is illustrative:

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Methylene-bridged alcohols similar to Guerbet alcohols and suitable for use herein can also be made by the hydroformylation of internal olefins, preferably using a catalyst that avoids or minimizes the degree of isomerization of the carbon-carbon double bond (see, e.g., Frankel, J. Am. Oil. Chem. Soc. 48 (1971) 248). Internal olefins can be made numerous ways, including, for instance by self-metathesis of alpha-olefins. The synthesis of 2-hexyl-1-nonanol from 1-octene illustrates this approach:

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Methylene-bridged alcohols suitable for use can also be made in a multi-step synthesis starting from an aldehyde, which is converted to an imine (e.g., with cyclohexylamine), deprotonated, alkylated, deprotected, and then reduced to give the desired alcohol. The synthesis of 2-heptyl-1-decanol from nonanal and 1-bromooctane, which is detailed below in the experimental section, is an example:

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Methylene-bridged alcohols suitable for use can also be made by the hydroboration of vinylidenes produced by dimerizing alpha-olefins. Both the olefin dimerization reaction and hydroboration/oxidation steps are highly selective. The olefin dimerization step to produce the vinylidene can be catalyzed by alkylaluminum compounds (see, e.g., U.S. Pat. Nos. 3,957,664, 4,973,788, 5,625,105, 5,659,100, 6,566,319, and references cited therein, the teachings of which are incorporated herein by reference), metallocene/alumoxane mixtures (see, e.g., U.S. Pat. No. 4,658,078), or the like. Hydroboration and oxidation proceeds with diborane to give almost exclusively the primary alcohol (see H. C. Brown, Hydroboration (1962) W. A. Benjamin, pp. 12-13, 114-115). The preparation of 2-hexyl-1-decanol from 1-octene illustrates this approach:

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The vinylidenes can also be used to make the dimethylene (—CH₂CH₂—) bridged alcohols. Dimethylene-bridged alcohols can be made, for instance, by the hydroformylation of vinylidenes using catalysts that minimize isomerization and production of methyl-branched isomers. Although methyl branching has been considered advantageous for enhancing biodegradability (see PCT Int. Appl. No. WO 2013/181083), the objective here is to maximize formation of product having mid-chain polar groups and to minimize other products, including the methyl-branched hydroformylation products. Suitable hydroformylation catalysts and reaction conditions for selectively adding the CO to the vinylidene terminus are disclosed in GB 2451325 and U.S. Pat. Nos. 3,952,068 and 3,887,624, the teachings of which are incorporated herein by reference. For instance:

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Dimethylene-bridged alcohols can also be made by simply heating the vinylidene with paraformaldehyde (or another source of formaldehyde), followed by catalytic hydrogenation of the resulting mixture of allylic alcohols (one regioisomer shown below) according to the method taught by Kashimura et al. (JP 2005/298443):

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The alcohol sulfates are conveniently made by reacting the corresponding alkylene-bridged alcohol with a sulfating agent according to known methods (see, e.g., U.S. Pat. No. 3,544,613, the teachings of which are incorporated herein by reference). Sulfamic acid is a convenient reagent that sulfates the hydroxyl group without disturbing any unsaturation present in the alkyl chain. Thus, warming the alcohol with sulfamic acid optionally in the presence of urea or another proton acceptor conveniently provides the desired alkyl ammonium sulfate. The ammonium sulfate is easily converted to an alkali metal sulfate by reaction with an alkali metal hydroxide (e.g., sodium hydroxide) or other ion-exchange reagents (see preparation of sodium 2-hexyl-1-decyl sulfate, below). Other suitable sulfating agents include sulfur trioxide, oleum, and chlorosulfonic acid.

When an alcohol alkoxylate is desired, the alcohol precursor is reacted with ethylene oxide, propylene oxide, butylene oxide, or the like, or mixtures thereof, usually in the presence of a base (e.g., KOH), a double metal cyanide (DMC) complex (see, e.g., U.S. Pat. No. 5,482,908), or other catalyst, to add a desired average number of oxyalkylene units. Ethylene oxide is particularly preferred. Typically, the number of oxyalkylene units ranges from 0.5 to 100, preferably from 1 to 30, more preferably from 1 to 10.

When an ether sulfate is desired, the alcohol precursor is first alkoxylated as described above. Sulfation of the alcohol alkoxylate (usually an alcohol ethoxylate) gives the desired ether sulfate.

In one aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol alkoxylate, or an ether sulfate of a C₁₄fatty alcohol. Preferred alcohols in this group include, for example, 2-hexyl-1-octanol, 2-pentyl-1-nonanol, 2-butyl-1-decanol, 2-propyl-1-undecanol, 3-pentyl-1-nonanol, 3-butyl-1-decanol, 3-propyl-1-undecanol, and mixtures thereof.

In another aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol alkoxylate, or an ether sulfate of a Cm fatty alcohol. Preferred alcohols in this group include, for example, 2-hexyl-1-nonanol, 2-pentyl-1-decanol, 2-butyl-1-undecanol, 3-hexyl-1-nonanol, 3-pentyl-1-decanol, 3-butyl-1-undecanol, 3-propyl-1-dodecanol, and mixtures thereof.

In another aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol ethoxylate, or an ether sulfate of a Cm fatty alcohol. Preferred alcohols in this group include, for example, 2-heptyl-1-nonanol, 2-hexyl-1-decanol, 2-pentyl-1-undecanol, 2-butyl-1-dodecanol, 3-hexyl-1-decanol, 3-pentyl-1-undecanol, 3-butyl-1-dodecanol, and mixtures thereof.

In another aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol alkoxylate, or an ether sulfate of a C₁₇fatty alcohol. Preferred alcohols in this group include, for example, 2-heptyl-1-decanol, 2-hexyl-1-undecanol, 2-pentyl-1-dodecanol, 3-heptyl-1-decanol, 3-hexyl-1-undecanol, 3-pentyl-1-dodecanol, 3-butyl-1-tridecanol, and mixtures thereof.

In another aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol alkoxylate, or an ether sulfate of a C₁₈fatty alcohol. Preferred alcohols in this group include, for example, 2-octyl-1-decanol, 2-heptyl-1-undecanol, 2-hexyl-1-dodecanol, 2-pentyl-1-tridecanol, 3-heptyl-1-undecanol, 3-hexyl-1-dodecanol, 3-pentyl-1-tridecanol, and mixtures thereof.

In yet another aspect, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol alkoxylate, or an ether sulfate of a C₁₉fatty alcohol. Preferred alcohols in this group include, for example, 2-octyl-1-undecanol, 2-heptyl-1-dodecanol, 2-hexyl-1-tridecanol, 3-octyl-1-undecanol, 3-heptyl-1-dodecanol, 3-hexyl-1-tridecanol, 3-pentyl-1-tetradecanol, and mixtures thereof.

In other preferred aspects, the alkylene-bridged surfactant includes, in addition to the polar group, a C₁₄-C₁₉alkyl moiety that includes a C₁₂-C₁₈alkyl chain and a C₁-C₂alkylene group bonded to a central zone carbon of the C₁₂-C₁₈alkyl chain. Preferred C₁₄alkyl moieties include, for example, 2-hexyl-1-octyl, 2-pentyl-1-nonyl, 2-butyl-1-decyl, 2-propyl-1-undecyl, 3-pentyl-1-nonyl, 3-butyl-1-decyl, and 3-propyl-1-undecyl. Preferred C₁₅alkyl moieties include, for example, 2-hexyl-1-nonyl, 2-pentyl-1-decyl, 2-butyl-1-undecyl, 3-hexyl-1-nonyl, 3-pentyl-1-decyl, 3-butyl-1-undecyl, and 3-propyl-1-dodecyl. Preferred C₁₆alkyl moieties include, for example, 2-heptyl-1-nonyl, 2-hexyl-1-decyl, 2-pentyl-1-undecyl, 2-butyl-1-dodecyl, 3-hexyl-1-decyl, 3-pentyl-1-undecyl, and 3-butyl-1-dodecyl. Preferred C₁₇alkyl moieties include, for example, 2-heptyl-1-decyl, 2-hexyl-1-undecyl, 2-pentyl-1-dodecyl, 3-heptyl-1-decyl, 3-hexyl-1-undecyl, 3-pentyl-1-dodecyl, and 3-butyl-1-tridecyl. Preferred C₁₈alkyl moieties include, for example, 2-octyl-1-decyl, 2-heptyl-1-undecyl, 2-hexyl-1-dodecyl, 2-pentyl-1-tridecyl, 3-heptyl-1-undecyl, 3-hexyl-1-dodecyl, and 3-pentyl-1-tridecyl. Preferred C₁₉alkyl moieties include, for example, 2-octyl-1-undecyl, 2-heptyl-1-dodecyl, 2-hexyl-1-tridecyl, 3-octyl-1-undecyl, 3-heptyl-1-dodecyl, 3-hexyl-1-tridecyl, and 3-pentyl-1-tetradecyl.

Suitable sulfonates can be made by reacting olefins with a sulfonating or sulfitating agent. The unsaturation in the olefin is preferably in a C₁-C₂branching group. For instance, the vinylidenes described earlier have the unsaturation in a C₁branching group. Suitable olefins having unsaturation in a C₂branching group can be made by hydroformylating vinylidenes, followed by dehydration of the alcohol product.

Sulfonation is performed using well-known methods, including reacting the olefin with sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid, or other known sulfonating agents. Chlorosulfonic acid is a preferred sulfonating agent. The sultones that are the immediate products of reacting olefins with S03, chlorosulfonic acid, and the like may be subsequently subjected to hydrolysis and neutralization with aqueous caustic to afford mixtures of alkene sulfonates and hydroxyalkane sulfonates. Suitable methods for sulfonating olefins are described in U.S. Pat. Nos. 3,169,142; 4,148,821; and U.S. Pat. Appl. Publ. No. 2010/0282467, the teachings of which are incorporated herein by reference. As noted above, vinylidenes can be used as starting materials for the sulfonation; GB 1139158, e.g., teaches sulfonation of 2-hexyl-1-decene to make a product comprising mostly alkene sulfonates.

Sulfitation is accomplished by combining an olefin in water (and usually a cosolvent such as isopropanol) with at least a molar equivalent of a sulfitating agent using well-known methods. Suitable sulfitating agents include, for example, sodium sulfite, sodium bisulfite, sodium metabisulfite, or the like. Optionally, a catalyst or initiator is included, such as peroxides, iron, or other free-radical initiators. Typically, the reaction is conducted at 15-100° C. until reasonably complete. Suitable methods for sulfitating olefins appear in U.S. Pat. Nos. 2,653,970; 4,087,457; 4,275,013, the teachings of which are incorporated herein by reference.

Sulfonation or sulfitation of the olefins may provide reaction products that include one or more of alkanesulfonates, alkenesulfonates, sultones, and hydroxy-substituted alkanesulfonates. The scheme below illustrates hydroxy-substituted alkanesulfonates and alkenesulfonates that can be generated from sulfonation of the C₂-branched olefin:

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Alkylene-bridged arylsulfonates can be made by alkylating arenes such as benzene, toluene, xylenes, or the like, with vinylidenes or other olefins having unsaturation in a C₁-C₂branching group, followed by sulfonation of the aromatic ring and neutralization.

Suitable alcohol phosphates can be made by reacting the alcohol precursors or the alcohol alkoxylates described above with phosphoric anhydride, polyphosphoric acid, or the like, or mixtures thereof according to well-known methods. See, for example, D. Tracy et al., J. Surf. Det. 5 (2002) 169 and U.S. Pat. Nos. 6,566,408; 5,463,101; and 5,550,274, the teachings of which are incorporated herein by reference.

The alcohol precursors to alkylene-bridged surfactants mentioned above can be converted to the corresponding primary, secondary, or tertiary amines by an amination process. In some cases, it may be more desirable to make the amines through an intermediate such as a halide or other compound having a good leaving group. Amination is preferably performed in a single step by reacting the corresponding fatty alcohol with ammonia or a primary or secondary amine in the presence of an amination catalyst. Suitable amination catalysts are well known. Catalysts comprising copper, nickel, and/or alkaline earth metal compounds are common. For suitable catalysts and processes for amination, see U.S. Pat. Nos. 5,696,294; 4,994,622; 4,594,455; 4,409,399; and 3,497,555, the teachings of which are incorporated herein by reference.

The alkylene-bridged amine oxides and quaterniums are conveniently available from the corresponding tertiary amines by oxidation or quaternization. The alkylene-bridged betaines and sulfobetaines are conveniently available from the corresponding tertiary amines by reaction with, e.g., sodium monochloroacetate (betaines) or sodium metabisulfite and epichlorohydrin in the presence of base (sulfobetaines). For examples of how to prepare quaterniums, betaines, and sulfobetaines, see PCT Int. Publ. No. WO2012/061098, the teachings of which are incorporated herein by reference. An illustrative sequence:

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The method of the invention provides improved cold-water cleaning performance. Details of the procedure appear in the experimental section below. The inventive method can provide an SRI improvement of at least 0.5 units, preferably at least 1.0 unit, and more preferably at least 2.0 units at the same wash temperature less than 30° C. on at least one greasy soil when compared with the SRI provided by a similar cold-water cleaning method in which the detergent comprises a primary surfactant other than the alkylene-bridged surfactant. Herein, we compare performance of the alkylene-bridged surfactant with primary surfactants currently used in cold-water detergents. In particular, the comparative surfactants are a sodium C₁₂-C₁₄alcohol ethoxylate sulfate (Na AES) or a sodium linear alkylbenzene sulfonate (Na LAS) as shown in the examples below.

In another aspect, the invention relates to a liquefaction method. The method comprises liquefying a greasy soil in water at a temperature less than 30° C., preferably 5° C. to 25° C., in the presence of a detergent comprising a well-defined mid-chain, alkylene-bridged headgroup surfactant. The surfactant has (a) a saturated or unsaturated, linear or branched C₁₂-C₁₈alkyl chain; (b) a polar group; and (c) a C₁-C₂alkylene group bonded to the polar group and a central zone carbon of the C₁₂-C₁₈alkyl chain. The surfactant also has, excluding the polar group, a total of 14 to 19 carbons. The greasy soil is, for example, bacon grease, beef tallow, butter, cooked beef fat, solid oil, vegetable oils, vegetable wax, petroleum wax, or the like, or mixtures thereof. In some aspects, the greasy soil has a melting point at or above the temperature of the water used for washing. Thus, in some aspects, the greasy soil has a melting point of at least 5° C., preferably at least 30° C. Suitable alkylene-bridged surfactants have already been described. Preferred surfactants include alcohol sulfates, alcohol alkoxylates, ether sulfates, sulfonates, arylsulfonates, alcohol phosphates, amine oxides, quaterniums, betaines, sulfobetaines, or mixtures thereof. Particularly preferred alkylene-bridged surfactants are alcohol sulfates, alcohol alkoxylates, or ether sulfates, especially alcohol sulfates. In certain aspects, the alkylene-bridged surfactant is an alcohol sulfate, an alcohol ethoxylate, or an ether sulfate of a C₁₆or C₁₇fatty alcohol selected from 2-heptyl-1-nonanol, 2-hexyl-1-decanol, 2-pentyl-1-undecanol, 2-butyl-1-dodecanol, 3-hexyl-1-decanol, 3-pentyl-1-undecanol, 3-butyl-1-dodecanol, 2-heptyl-1-decanol, 2-hexyl-1-undecanol, 2-pentyl-1-dodecanol, 3-heptyl-1-decanol, 3-hexyl-1-undecanol, 3-pentyl-1-dodecanol, and 3-butyl-1-tridecanol.

We surprisingly found, as shown in Table 8 below, that detergents comprising the alkylene-bridged surfactants have exceptional ability to liquefy greasy soils at temperatures well below their melting points. In a simple experiment, solid beef tallow is smeared on a glass slide and covered with a glass slide cover. Aqueous solutions containing dilute (0.1 wt. %) alkylene-bridged surfactant or a control are applied to the interface between the slide cover and slide. In this static test at 15° C., all of the work is done by the surfactant; there is no heat or mechanical action available to assist in loosening the soil. The interface is inspected under a microscope to observe any changes. In the control example, none of the beef tallow is liquefied; essentially no changes are evident at the interface. In contrast, when the alkylene-bridged surfactant is tested, globules of beef tallow form and migrate away from the interface within 5 to 10 minutes. The results demonstrate the unusual efficacy of the alkylene-bridged surfactants for liquefying greasy soils even in cold water.

In certain preferred aspects, the detergent compositions further comprise a nonionic surfactant, which is preferably a fatty alcohol ethoxylate.

In another preferred aspect, the detergent is in the form of a liquid, powder, paste, granule, tablet, or molded solid, or a water-soluble sheet, sachet, capsule, or pod.

In another preferred aspect, the detergent comprises 1 to 70 wt. %, preferably 5 to 15 wt. %, of a fatty alcohol ethoxylate, 1 to 70 wt. %, preferably 1 to 20 wt. %, of the alkylene-bridged surfactant, and 1 to 70 wt. %, preferably 5 to 15 wt. %, of anionic surfactant selected from linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, and fatty alcohol sulfates.

In one aspect, the detergent may comprise an alkylene-bridged surfactant, water, a solvent, a hydrotrope, an auxiliary surfactant, or mixtures thereof. The solvent and/or auxiliary surfactant and hydrotrope usually help to compatibilize a mixture of water and the alkylene-bridged surfactant. An “incompatible” mixture of water and an alkylene-bridged surfactant (absent a solvent and/or auxiliary) is opaque at temperatures between about 15° C. and 25° C. This product form is difficult to ship and difficult to formulate into commercial detergent formulations. In contrast, a “compatible” mixture of water and alkylene-bridged surfactant is transparent or translucent, and it flows readily when poured or pumped at temperatures within the range of about 15° C. to 25° C. This product form provides ease of handling, shipping, and formulating from a commercial perspective.

Suitable solvents include, for example, isopropanol, ethanol, 1-butanol, ethylene glycol n-butyl ether, the Dowanol® series of solvents, propylene glycol, butylene glycol, propylene carbonate, ethylene carbonate, solketal, and the like. Preferably, the composition should comprise less than 25 wt. %, more preferably less than 15 wt. %, and most preferably less than 10 wt. % of the solvent (based on the combined amounts of alkylene-bridged surfactant, solvent, hydrotrope, and any auxiliary surfactant).

Hydrotropes have the ability to increase the water solubility of organic compounds that are normally only slightly soluble in water. Suitable hydrotropes for formulating detergents for cold water cleaning are preferably short-chain surfactants that help to solubilize other surfactants. Preferred hydrotropes for use herein include, for example, aryl sulfonates (e.g., cumene sulfonates, xylene sulfonates), short-chain alkyl carboxylates, sulfosuccinates, urea, short-chain alkyl sulfates, short-chain alkyl ether sulfates, and the like, and combinations thereof. When a hydrotrope is present, the composition preferably comprises less than 25 wt. %, more preferably less than 10 wt. % of the hydrotrope (based on the combined amounts of alkylene-bridged surfactant, solvent, hydrotrope, and any auxiliary surfactant).

Suitable auxiliary surfactants include, for example, N,N-diethanol oleamide, N,N-diethanol C₈to C₁₈saturated or unsaturated fatty amides, ethoxylated fatty alcohols, alkyl polyglucosides, alkyl amine oxides, N,N-dialkyl fatty amides, oxides of N,N-dialkyl aminopropyl fatty amides, N,N-dialkyl aminopropyl fatty amides, alkyl betaines, linear C₁₂-C₁₈sulfates or sulfonates, alkyl sulfobetaines, alkylene oxide block copolymers of fatty alcohols, alkylene oxide block copolymers, and the like. Preferably, the composition should comprise less than 25 wt. %, more preferably less than 15 wt. %, and most preferably less than 10 wt. % of the auxiliary surfactant (based on the combined amounts of alkylene-bridged surfactant, auxiliary surfactant, and any solvent).

In other preferred aspects, the cold-water cleaning method is performed using particular laundry detergent formulations comprising alkylene-bridged surfactants.

One such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant and has a pH within the range of 7 to 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant and has a pH within the range of 7 to 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

a sufficient amount of one or two enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, and derivatives thereof.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant, has a pH within the range of 7 to 10, and is substantially free of enzymes. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant; and

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate.

1 to 70 wt. %, preferably 4 to 50 wt. %, of at least one C₁₆α-methyl ester sulfonate; and

0 to 70 wt. % of cocamide diethanolamine.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 5 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant and has a pH greater than 10. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

0.1 to 5 wt. % of metasilicate.

0 to 70 wt. %, preferably 0 to 50 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 25 wt. %, of at least one alcohol ether sulfate; and

0.1 to 20 wt. % of sodium carbonate.

Another such laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant. This detergent further comprises:

2 to 70 wt. %, preferably 2 to 40 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 32 wt. %, of at least one alcohol ether sulfate;

0 to 65 wt. %, preferably 0 to 25 wt. %, of at least one C₁₆α-methyl ester sulfonate;

0 to 6 wt. % of lauryl dimethylamine oxide;

0 to 6 wt. % of C₁₂EO₃;

0 to 10 wt. % of coconut fatty acid;

0 to 3 wt. % of borax pentahydrate;

0 to 6 wt. % of propylene glycol;

0 to 10 wt. % of sodium citrate;

0 to 6 wt. % of triethanolamine;

0 to 6 wt. % of monoethanolamine;

0 to 1 wt. % of at least one fluorescent whitening agent;

0 to 1.5 wt. % of at least one anti-redeposition agent;

0 to 2 wt. % of at least one thickener;

0 to 2 wt. % of at least one thinner;

0 to 2 wt. % of at least one protease;

0 to 2 wt. % of at least one amylase; and

0 to 2 wt. % of at least one cellulase.

Yet another such laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant. This detergent further comprises:

2 to 70 wt. %, preferably 2 to 40 wt. %, of at least one nonionic surfactant;

0 to 70 wt. %, preferably 0 to 32 wt. %, of at least one alcohol ether sulfate;

0 to 6 wt. % of lauryl dimethylamine oxide;

0 to 6 wt. % of C₁₂EO₃;

0 to 10 wt. % of coconut fatty acid;

0 to 10 wt. % of sodium metasilicate;

0 to 10 wt. % of sodium carbonate;

0 to 1 wt. % of at least one fluorescent whitening agent;

0 to 1.5 wt. % of at least one anti-redeposition agent;

0 to 2 wt. % of at least one thickener; and

0 to 2 wt. % of at least one thinner.

Another “green” laundry detergent composition comprises 1 to 95 wt. %, preferably 2 to 95 wt. %, of a detergent comprising an alkylene-bridged surfactant. This detergent further comprises:

0 to 70 wt. %, preferably 0 to 30 wt. %, of at least one C₁₆methyl ester sulfonate;

0 to 70 wt. %, preferably 0 to 30 wt. %, of at least one C₁₂methyl ester sulfonate;

0 to 70 wt. %, preferably 0 to 30 wt. %, of sodium lauryl sulfate;

0 to 30 wt. % of sodium stearoyl lactylate;

0 to 30 wt. % of sodium lauroyl lactate;

0 to 70 wt. %, preferably 0 to 60 wt. %, of alkyl polyglucoside;

0 to 70 wt. %, preferably 0 to 60 wt. %, of polyglycerol monoalkylate;

0 to 30 wt. % of lauryl lactyl lactate;

0 to 30 wt. % of saponin;

0 to 30 wt. % of rhamnolipid;

0 to 30 wt. % of sphingolipid;

0 to 30 wt. % of glycolipid;

0 to 30 wt. % of at least one abietic acid derivative; and

0 to 30 wt. % of at least one polypeptide.

In one aspect, the alkylene-bridged surfactant is used in a laundry pre-spotter composition. In this application, greasy or oily soils on the garments or textile fabrics are contacted directly with the pre-spotter in advance of laundering either manually or by machine. Preferably, the fabric or garment is treated for 5-30 minutes. The amount of active alkylene-bridged surfactant in the pre-spotter composition is preferably 0.5 to 50 wt. %, more preferably 1 to 30 wt. %, and most preferably 5 to 20 wt. %. Treated fabric is machine laundered as usual, preferably at a temperature within the range of 5° C. and 30° C., more preferably 10° C. to 20° C., most preferably 12° C. to 18° C.

In another aspect, the alkylene-bridged surfactant is used in a pre-soaker composition for manual or machine washing.

When used for manual washing, the pre-soaker composition is combined with cold water in a washing tub or other container. The amount of active alkylene-bridged surfactant in the pre-soaker composition is preferably 0.5 to 100 wt. %, more preferably 1 to 80 wt. %, and most preferably 5 to 50 wt. %. Garments or textile fabrics are preferably saturated with pre-soaker in the tub, allowed to soak for 15-30 minutes, and laundered as usual.

When used for machine washing, the pre-soaker composition is preferably added to a machine containing water at a temperature within the range of 5° C. and 30° C., more preferably 10° C. to 20° C., most preferably 12° C. to 18° C. The amount of active alkylene-bridged surfactant in the pre-soaker composition is preferably 0.5 to 100 wt. %, more preferably 1 to 80 wt. %, and most preferably 5 to 50 wt. %. Garments/textile fabrics are added to the machine, allowed to soak (usually with a pre-soak cycle selected on the machine) for 5-10 minutes, and then laundered as usual.

In another aspect, the alkylene-bridged surfactant is used as an additive for a laundry product or formulation. In such applications, the surfactant helps to improve or boost the grease removal or grease cutting performance of the laundry product or formulation. Preferably, the amount of alkylene-bridged surfactant actives used will be within the range of 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 3 to 5 wt. %. The laundry product or formulation and the alkylene-bridged surfactant are preferably mixed until a homogeneous composition is obtained.

In yet another aspect, the alkylene-bridged surfactant is used as a surfactant additive. In such applications, the resulting modified surfactant will have improved grease removal or grease cutting properties. Preferably, the amount of alkylene-bridged surfactant actives used will be within the range of 1 to 10 wt. %, more preferably 2 to 8 wt. %, and most preferably 3 to 5 wt. %. The resulting modified surfactant will help to achieve improved grease cutting/removal in commercial products. Such products may be used at a temperature within the range of 5° C. and 30° C., preferably 10° C. to 20° C., and more preferably 12° C. to 18° C.

General Considerations for Laundry Detergents

Desirable surfactant attributes for laundry detergents include having the ability to be formulated as heavy duty liquid (HDL) detergents, powders, bar soaps, sachets, pods, capsules, or other detergents forms.

For HDLs, this includes being in liquid form at room temperature, an ability to be formulated in cold-mix applications, and an ability to perform as well as or better than existing surfactants.

Desirable attributes for HDLs include, for example, the ability to emulsify, suspend or penetrate greasy or oily soils and suspend or disperse particulates, in order to clean surfaces; and then prevent the soils, grease, or particulates from re-depositing on the newly cleaned surfaces.

It is also desirable to have the ability to control the foaming. For use of an HDL in a high efficiency washing machine, low foam is desired to achieve the best cleaning and to avoid excess foaming. Other desirable properties include the ability to clarify the formulation and to improve long-term storage stability under both extreme outdoor and normal indoor temperatures.

The skilled person will appreciate that the surfactants of the present disclosure will usually not be mere “drop-in” substitutions in an existing detergent formulation. Some amount of re-formulation is typically necessary to adjust the nature and amounts of other surfactants, hydrotropes, alkalinity control agents, and/or other components of the formulation in order to achieve a desirable outcome in terms of appearance, handling, solubility characteristics, and other physical properties and performance attributes. For example, a formulation might need to be adjusted by using, in combination with the mid-chain headgroup or alkylene-bridged surfactant, a more highly ethoxylated nonionic surfactant instead of one that has fewer EO units. This kind of reformulating is considered to be within ordinary skill and is left to the skilled person's discretion.

A wide variety of detergent compositions can be made that include the mid-chain headgroup or alkylene-bridged surfactants, with or without other ingredients as specified below. Formulations are contemplated including 1% to 99% mid-chain headgroup or alkylene-bridged surfactant, more preferably between 1% and 60%, even more preferably between 1% and 30%, with 99% to 1% water and, optionally, other ingredients as described here.

Additional Surfactants

The detergent compositions can contain co-surfactants, which can be anionic, cationic, nonionic, ampholytic, zwitterionic, or combinations of these.

Anionic Surfactants

Formulations of the invention can include anionic surfactants in addition to the mid-chain headgroup or alkylene-bridged surfactant. “Anionic surfactants” are defined here as amphiphilic molecules with an average molecular weight of less than about 10,000, comprising one or more functional groups that exhibit a net anionic charge when present in aqueous solution at the normal wash pH, which can be a pH between 6 and 11. The anionic surfactant can be any anionic surfactant that is substantially water soluble. “Water soluble” surfactants are, unless otherwise noted, here defined to include surfactants which are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25° C. At least one of the anionic surfactants used may be an alkali or alkaline earth metal salt of a natural or synthetic fatty acid containing between about 4 and about 30 carbon atoms. A mixture of carboxylic acid salts with one or more other anionic surfactants can also be used. Another important class of anionic compounds is the water soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to about 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.

Specific types of anionic surfactants are identified in the following paragraphs. In some aspects, alkyl ether sulfates are preferred. In other aspects, linear alkyl benzene sulfonates are preferred.

Carboxylic acid salts are represented by the formula:

R¹COOM

where R¹is a primary or secondary alkyl group of 4 to 30 carbon atoms and M is a solubilizing cation. The alkyl group represented by R¹may represent a mixture of chain lengths and may be saturated or unsaturated, although it is preferred that at least two thirds of the R¹groups have a chain length of between 8 and 18 carbon atoms. Non-limiting examples of suitable alkyl group sources include the fatty acids derived from coconut oil, tallow, tall oil and palm kernel oil. For the purposes of minimizing odor, however, it is often desirable to use primarily saturated carboxylic acids. Such materials are well known to those skilled in the art, and are available from many commercial sources, such as Uniqema (Wilmington, Del.) and Twin Rivers Technologies (Quincy, Mass.). The solubilizing cation, M, may be any cation that confers water solubility to the product, although monovalent such moieties are generally preferred. Examples of acceptable solubilizing cations for use with the present technology include alkali metals such as sodium and potassium, which are particularly preferred, and amines such as triethanolammonium, ammonium and morpholinium. Although, when used, the majority of the fatty acid should be incorporated into the formulation in neutralized salt form, it is often preferable to leave a small amount of free fatty acid in the formulation, as this can aid in the maintenance of product viscosity.

Primary alkyl sulfates are represented by the formula:

R²OSO₃M

where R²is a primary alkyl group of 8 to 18 carbon atoms and can be branched or linear, saturated or unsaturated. M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). The alkyl group R²may have a mixture of chain lengths. It is preferred that at least two-thirds of the R²alkyl groups have a chain length of 8 to 18 carbon atoms. This will be the case if R²is coconut alkyl, for example. The solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. An alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.

Alkyl ether sulfates are represented by the formula:

R³O(CH₂CH₂O)_nSO₃M

where R³is a primary alkyl group of 8 to 18 carbon atoms, branched or linear, saturated or unsaturated, and n has an average value in the range from 1 to 6 and M is a solubilizing cation. The alkyl group R³may have a mixture of chain lengths. It is preferred that at least two-thirds of the R³alkyl groups have a chain length of 8 to 18 carbon atoms. This will be the case if R³is coconut alkyl, for example. Preferably n has an average value of 2 to 5. Ether sulfates have been found to provide viscosity build in certain of the formulations of the present technology, and thus are considered a preferred ingredient.

Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of C₈-C₂₀carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO₃(see, e.g., J. Am. Oil Chem. Soc. 52 (1975) 323). Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:

R³—CH(SO₃M)-C(O)—OR⁴

where R³is a C₆-C₂₀hydrocarbyl, preferably an alkyl or combination thereof R⁴is a C₁-C₆hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation that forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. The group R³may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R³CH(−)CO₂(−) is derived from a coconut source, for instance. Preferably, R³is C₁₀-C₁₆alkyl, and R⁴is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates where R³is C₁₀-C₁₆alkyl.

Alkyl benzene sulfonates are represented by the formula:

R⁶ArSO₃M

where R⁶is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring (—C₆H₄—) and M is a solubilizing cation. The group R⁶may be a mixture of chain lengths. A mixture of isomers is typically used, and a number of different grades, such as “high 2-phenyl” and “low 2-phenyl” are commercially available for use depending on formulation needs. Many commercial suppliers exist for these materials, including Stepan, Akzo, Pilot, and Rhodia. Typically, they are produced by the sulfonation of alkylbenzenes, which can be produced by either the HF-catalyzed alkylation of benzene with olefins or an AlCl₃-catalyzed process that alkylates benzene with chloroparaffins, and are sold by, for example, Petresa (Chicago, Ill.) and Sasol (Austin, Tex.). Straight chains of 11 to 14 carbon atoms are usually preferred.

Paraffin sulfonates having about 8 to about 22 carbon atoms, preferably about 12 to about 16 carbon atoms, in the alkyl moiety, are contemplated for use here. They are usually produced by the sulfoxidation of petrochemically derived normal paraffins. These surfactants are commercially available as, for example, Hostapur SAS from Clariant (Charlotte, N.C.).

Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, are also contemplated for use in the present compositions. The olefin sulfonates are further characterized as having from 0 to 1 ethylenic double bonds; from 1 to 2 sulfonate moieties, of which one is a terminal group and the other is not; and 0 to 1 secondary hydroxyl moieties. U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates, and its teachings are incorporated herein by reference. Such materials are sold as, for example, Bio-Terge® AS-40, a product of Stepan.

Sulfosuccinate esters represented by the formula:

R⁷OOCCH₂CH(SO₃⁻M⁺)COOR⁸

are also useful herein as anionic surfactants. R⁷and R⁸are alkyl groups with chain lengths of between 2 and 16 carbons, and may be linear or branched, saturated or unsaturated. A preferred sulfosuccinate is sodium bis(2-ethylhexyl)sulfosuccinate, which is commercially available under the trade name Aerosol OT from Cytec Industries (West Paterson, N.J.).

Organic phosphate-based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl-terminated alkoxide condensates, or salts thereof. Suitable organic phosphate esters include phosphate esters of polyoxyalkylated alkylaryl phenols, phosphate esters of ethoxylated linear alcohols, and phosphate esters of ethoxylated phenols. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.

Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C₈-C₂₂primary of secondary alkanesulfonates, C₈-C₂₄olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Pat. No. 1,082,179, C₈-C₂₄alkyl poly glycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C₆-C₁₂diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic non-sulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)_kCH₂COO-M+ where R is a C₈-C₂₂alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. Nos. 3,929,678 and 6,949,498, the teachings of which are incorporated herein by reference.

Other anionic surfactants contemplated include isethionates, sulfated triglycerides, alcohol sulfates, ligninsulfonates, naphthelene sulfonates and alkyl naphthelene sulfonates, and the like.

Specific anionic surfactants contemplated for use in the present compositions include alcohol ether sulfates (AES), linear alkylbenzene sulfonates (LAS), alcohol sulfates (AS), alpha methyl ester sulfonates (MES), or combinations of two or more of these. The amount of anionic surfactant contemplated can be, for example, 1% to 70% of the composition more preferably between 1% and 60%, even more preferably between 1% and 40%. For a more general description of surfactants, see U.S. Pat. No. 5,929,022, the teachings of which are incorporated herein by reference.

Nonionic or Ampholytic Surfactants

Examples of suitable nonionic surfactants include alkyl polyglucosides (“APGs”), alcohol ethoxylates, nonylphenol ethoxylates, methyl ester ethoxylates (“MEEs”), and others. The nonionic surfactant may be used as from 1% to 90%, more preferably from 1 to 40% and most preferably between 1% and 32% of a detergent composition. Other suitable nonionic surfactants are described in U.S. Pat. No. 5,929,022, from which much of the following discussion comes.

One class of nonionic surfactants useful herein are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For “low HLB” nonionics, low HLB can be defined as having an HLB of 8 or less and preferably 6 or less. A “low level” of co-surfactant can be defined as 6% or less of the HDL and preferably 4% or less of the HDL.

Especially preferred nonionic surfactants of this type are the C₉-C₁₅primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C₁₂-C₁₅primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol. One suitable example of such a surfactant is polyalkoxylated aliphatic base, sold for example as Bio-Soft® N25-7 by Stepan Company.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula:

RO—(C_nH_2nO)_tZ_x

where Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x has an average value from 1.3 to 4. The compounds include less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0 070 077, EP 0 075 996 and EP 0 094 118.

Also suitable as nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

R²—C(O)—N(R¹)—Z

where R¹is H, or R¹is C₁-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R²is C₅-C₃₁hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹is methyl, R²is a straight C₁₁-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and where one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. Nos. 3,664,961 and 3,929,678, the teachings of which are incorporated herein by reference). Suitable ampholytic surfactants include fatty amine oxides, fatty amidopropylamine oxides, fatty betaines, and fatty amidopropylamine betaines. Examples of suitable betaines are coco betaine (CB) and cocoamidopropyl betaine (CAPB). Commercially available betaines include Amphosol® HCG or Amphosol® HCA (cocamidopropyl betaine) surfactants (Stepan). Suitable amine oxides include laurylamine oxide, myristylamine oxide, lauryl amidopropylamine oxide, myristyl amidopropylamine oxide, and the like, and mixtures thereof. Commercially available amine oxides include Ammonyx® LO, Ammonyx® MO, andAmmonyx® LMDO surfactants (Stepan).

Ampholytic surfactants can be used at a level from 1% to 50%, more preferably from 1% to 10%, even more preferably between 1% and 5% of the formulation, by weight.

Amine oxide surfactants are highly preferred. Compositions herein may comprise an amine oxide in accordance with the general formula:

R¹(EO)_x(PO)_y(BO)_zN(O)(CH₂R′)₂·H₂O

In general, it can be seen that the preceding formula provides one long-chain moiety R¹(EO)_x(PO)_y(BO)_zand two short chain moieties, —CH₂R′. R′ is preferably selected from hydrogen, methyl and —CH₂OH. In general R¹is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R¹is a primary alkyl moiety. When x+y+z=0, R¹is a hydrocarbyl moiety having a chain length of from about 8 to about 18. When x+y+z is different from 0, R¹may be somewhat longer, having a chain length in the range C₁₂-C₂₄. The general formula also encompasses amine oxides where x+y+z=0, R¹is C₈-C₁₈, R′ is H and q=from 0 to 2, preferably 2. These amine oxides are illustrated by C₁₂-C₁₄alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Pat. Nos. 5,075,501 and 5,071,594, the teachings of which are incorporated herein by reference.

Also suitable are amine oxides where x+y+z is different from zero. Specifically, x+y+z is from about 1 to about 10, and R¹is a primary alkyl group containing about 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms. In these embodiments y+z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.

Preferred amine oxides are solids at ambient temperature. More preferably, they have melting points in the range of 30° C. to 90° C. Amine oxides suitable for use are made commercially by Stepan, AkzoNobel, Procter & Gamble, and others. See McCutcheon's compilation and a Kirk-Othmer review article for alternate amine oxide manufacturers.

Suitable detergents may include, e.g., hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethylamine oxide, and tetradecyldimethylamine oxide dihydrate.

In certain aspects in which R′ is H, there is some latitude with respect to having R′ slightly larger than H. Specifically, R′ may be CH₂OH, as in hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide.

Zwitterionic Surfactants

Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and where one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. No. 3,664,961, the teachings of which are incorporated herein by reference). Zwitterionic surfactants can be used as from 1% to 50%, more preferably from 1% to 10%, even more preferably from 1% to 5% by weight of the present formulations.

Mixtures of any two or more individually contemplated surfactants, whether of the same type or different types, are contemplated herein.

Formulation and Use

Four desirable characteristics of a laundry detergent composition, in particular a liquid composition (although the present disclosure is not limited to a liquid composition, or to a composition having any or all of these attributes) are that (1) a concentrated formulation is useful to save on shelf space of a retailer, (2) a “green” or environmentally friendly composition is useful, (3) a composition that works in modern high efficiency washing machines which use less energy and less water to wash clothes than previous machines is useful, and (4) a composition that cleans well in cold water, i.e., less than 30° C., preferably 5° C. to 30° C.

To save a substantial amount of retailer shelf space, a concentrated formulation is contemplated having two or even three, four, five, six, or even greater (e.g., 8×) times potency per unit volume or dose as conventional laundry detergents. The use of less water complicates the formulation of a detergent composition, as it needs to be more soluble and otherwise to work well when diluted in relatively little water.

To make a “green” formula, the surfactants should be ultimately biodegradable and non-toxic. To meet consumer perceptions and reduce the use of petrochemicals, a “green” formula may also advantageously be limited to the use of renewable hydrocarbons, such as vegetable or animal fats and oils, in the manufacture of surfactants.

High efficiency (HE) washing machines present several challenges to the detergent formulation. As of January 2011, all washing machines sold in the U.S. must be HE, at least to some extent, and this requirement will only become more restrictive in the coming years. Front loading machines, all of which are HE machines, represent the highest efficiency, and are increasingly being used.

Heavy duty liquid detergent formulas are impacted by HE machines because the significantly lower water usage requires that less foam be generated during the wash cycle. As the water usage levels continue to decrease in future generations of HE machines, detergents may be required to transition to no foam. In addition, HE HDLs should also disperse quickly and cleanly at lower wash temperatures.

To work in a modern high efficiency washing machine, the detergent composition needs to work in relatively concentrated form in cold water, as these washing machines use relatively little water and cooler washing temperatures than prior machines. The sudsing of such high-efficiency formulations must also be reduced, or even eliminated, in a low-water environment to provide effective cleaning performance. The anti-redeposition properties of a high efficiency detergent formulation also must be robust in a low-water environment. In addition, formulations that allow the used wash water to be more easily rinsed out of the clothes or spun out of the clothes in a washing machine are also contemplated, to promote efficiency.

Liquid fabric softener formulations and “softergent” (fabric softener/detergent dual functional) single-add formulations also may need to change as water usage continues to decline in HE machines. A washer-added softener is dispensed during the rinse cycle in these machines. The mid-chain headgroup or alkylene-bridged surfactants can be used in formulations that provide softening in addition to cleaning.

Laundry detergents and additives containing the presently described mid-chain headgroup or alkylene-bridged surfactants are contemplated to provide high concentration formulations, or “green” formulations, or formulations that work well in high efficiency washing machines. Such detergents and additives are contemplated that have at least one of the advantages or desirable characteristics specified above, or combinations of two or more of these advantages, at least to some degree. The ingredients contemplated for use in such laundry detergents and additives are found in the following paragraphs.

In addition to the surfactants as previously described, a laundry detergent composition commonly contains other ingredients for various purposes. Some of those ingredients are also described below.

Builders and Alkaline Agents

Builders and other alkaline agents are contemplated for use in the present formulations.

Any conventional builder system is suitable for use here, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for environmental reasons, phosphate builders could also be used here.

Suitable polycarboxylate builders for use here include citric acid, preferably in the form of a water-soluble salt, and derivatives of succinic acid of the formula:

R—CH(COOH)CH₂(COOH)

where R is C_10-20alkyl or alkenyl, preferably C₁₂-C₁₆, or where R can be substituted with hydroxyl, sulfo, sulfoxyl, or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, or 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium, and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid, as described in U.S. Pat. No. 4,663,071.

Especially for a liquid detergent composition, suitable fatty acid builders for use here are saturated or unsaturated C₁₀-C₁₈fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.

Some examples of alkaline agents include alkali metal (Na, K, or NH₄) hydroxides, carbonates, citrates, and bicarbonates. Another commonly used builder is borax.

For powdered detergent compositions, the builder or alkaline agent typically comprises from 1% to 95% of the composition. For liquid compositions, the builder or alkaline agent typically comprises from 1% to 60%, alternatively between 1% and 30%, alternatively between 2% and 15%. See U.S. Pat. No. 5,929,022, the teachings of which are incorporated by reference, from which much of the preceding discussion comes. Other builders are described in PCT Int. Publ. WO 99/05242, which is incorporated here by reference.

Enzymes

The detergent compositions may further comprise one or more enzymes, which provide cleaning performance and/or fabric care benefits. The enzymes include cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases or mixtures thereof.

A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter of wash solution.

Suitable cellulases include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2 247 832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50,000, an isoelectric point of 5.5 and containing 415 amino acid units. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in EP Appl. No. 91202879.2.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for “solution bleaching”, i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT Int. Appl. WO 89/099813 and in EP Appl. No. 91202882.6.

The cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase®, Savinase®, Primase®, Durazym®, and Esperase® by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase®, Maxacal® and Maxapem® by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes. Other proteases are described in U.S. Pat. No. 5,679,630 can be included in the detergent compositions. Protease enzyme may be incorporated into the detergent compositions at a level of from about 0.0001% to about 2% active enzyme by weight of the composition.

A preferred protease here referred to as “Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in the carbonyl hydrolase equivalent to position+76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in U.S. Pat. No. 5,679,630, the teachings of which are incorporated herein by reference.

Highly preferred enzymes that can be included in the detergent compositions include lipases. It has been found that the cleaning performance on greasy soils is synergistically improved by using lipases. Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Pat. No. 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P “Amano,” hereafter referred to as “Amano-P.” Further suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades). Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in U.S. Pat. No. 6,017,871. Preferably, the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the detergent compositions at a level of from 50 LU to 8500 LU per liter wash solution. Preferably, the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution. A more preferred level is from 150 LU to 5000 LU per liter of wash solution.

By “D96L lipolytic enzyme variant,” we mean the lipase variant as described in PCT Int. Appl. WO 92/05249, where the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to leucine (L). According to this nomenclature, the substitution of aspartic acid to leucine in position 96 is shown as: D96L.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases that do not require interfacial activation. Addition of cutinases to detergent compositions is described, e.g. in PCT Int. Appl. No. WO 88/09367.

The lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Amylases (α and/or β) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® amylases (Novo Nordisk).

The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and/or yeast origin. See U.S. Pat. No. 5,929,022, the teachings of which are incorporated herein by reference, from which much of the preceding discussion comes. Preferred compositions optionally contain a combination of enzymes or a single enzyme, with the amount of each enzyme commonly ranging from 0.0001% to 2%.

Other enzymes and materials used with enzymes are described in PCT Int. Appl. No. WO99/05242, which is incorporated here by reference.

Adjuvants

The detergent compositions optionally contain one or more soil suspending agents or resoiling inhibitors in an amount from about 0.01% to about 5% by weight, alternatively less than about 2% by weight. Resoiling inhibitors include anti-redeposition agents, soil release agents, or combinations thereof. Suitable agents are described in U.S. Pat. No. 5,929,022, and include water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Examples of such soil release and anti-redeposition agents include an ethoxylated tetraethylenepentamine. Further suitable ethoxylated amines are described in U.S. Pat. No. 4,597,898, the teachings of which are incorporated herein by reference. Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in EP Appl. No. 111,965. Other clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in EP Appl. No. 111,984; the zwitterionic polymers disclosed in EP Appl. No. 112,592; and the amine oxides disclosed in U.S. Pat. No. 4,548,744, the teachings of which are incorporated herein by reference.

Other clay soil removal and/or anti-redeposition agents known in the art can also be utilized in the compositions hereof. Another type of preferred anti-redeposition agent includes the carboxymethylcellulose (CMC) materials.

Anti-redeposition polymers can be incorporated into HDL formulations described herein. It may be preferred to keep the level of anti-redeposition polymer below about 2%. At levels above about 2%, the anti-redeposition polymer may cause formulation instability (e.g., phase separation) and or undue thickening.

Soil release agents are also contemplated as optional ingredients in the amount of about 0.1% to about 5% (see, e.g., U.S. Pat. No. 5,929,022).

Chelating agents in the amounts of about 0.1% to about 10%, more preferably about 0.5% to about 5%, and even more preferably from about 0.8% to about 3%, are also contemplated as an optional ingredient (see, e.g., U.S. Pat. No. 5,929,022).

Polymeric dispersing agents in the amount of 0% to about 6% are also contemplated as an optional component of the presently described detergent compositions (see, e.g., U.S. Pat. No. 5,929,022).

Polyetheramines, such as the compositions described in U.S. Publ. No. 2015/0057212 can be included if desired, typically in amounts of 0.1 to 20 wt. %, if desired to modify or enhance cleaning performance.

A suds suppressor is also contemplated as an optional component of the present detergent composition, in the amount of from about 0.1% to about 15%, more preferably between about 0.5% to about 10% and even more preferably between about 1% to about 7% (see, e.g., U.S. Pat. No. 5,929,022).

Other ingredients that can be included in a liquid laundry detergent include perfumes, which optionally contain ingredients such as aldehydes, ketones, esters, and alcohols. More compositions that can be included are: carriers, hydrotropes, processing aids, dyes, pigments, solvents, bleaches, bleach activators, fluorescent optical brighteners, and enzyme stabilizing packaging systems.

The co-surfactants and fatty acids described in U.S. Pat. No. 4,561,998, the teachings of which are incorporated herein by reference, can be included in the detergent compositions. In conjunction with anionic surfactants, these improve laundering performance. Examples include chloride, bromide and methylsulfate C₈-C₁₆alkyl trimethylammonium salts, C₈-C₁₆alkyl di(hydroxyethyl) methylammonium salts, C₈-C₁₆alkyl hydroxyethyldimethylammonium salts, and C₈-C₁₆alkyloxypropyl trimethylammonium salts.

Similar to what is taught in U.S. Pat. No. 4,561,998, the compositions herein can also contain from about 0.25% to about 12%, preferably from about 0.5% to about 8%, more preferably from about 1% to about 4%, by weight of a cosurfactant selected from the group of certain quaternary ammonium, diquaternary ammonium, amine, diamine, amine oxide and di(amine oxide) surfactants. The quaternary ammonium surfactants are particularly preferred.

Quaternary ammonium surfactants can have the following formula:

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N+X⁻

wherein R²is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R³is selected from the group consisting of —CH₂CH₂—, —CH₂CH(CH₃)—, —CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—, and mixtures thereof; each R⁴is selected from the group consisting of C₁-C₄alkyl, C₁-C₄hydroxyalkyl, benzyl, ring structures formed by joining the two R⁴groups, —CH₂CHOHCHOHCOR⁶CHOHCH₂OH wherein R⁶is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵is the same as R⁴or is an alkyl chain wherein the total number of carbon atoms of R²plus R⁵is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above formula when R⁵is selected from the same groups as R⁴. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C₈-C₁₆alkyl trimethylammonium salts, C₈-C₁₆alkyl di(hydroxyethyl) methylammonium salts, C₈-C₁₆alkyl hydroxyethyldimethylammonium salts, and C₈-C₁₆alkyloxypropyl trimethylammonium salts. Of the above, decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate are particularly preferred.

U.S. Pat. No. 4,561,998 also provides that under cold water washing conditions, in this case less than about 65° F. (18.3° C.), the C₈-C₁₀alkyltrimethyl ammonium surfactants are particularly preferred since they have a lower Kraft boundary and, therefore, a lower crystallization temperature than the longer alkyl chain quaternary ammonium surfactants herein.

Diquaternary ammonium surfactants can be of the formula:

[R²(OR³)_y][R⁴OR³]_y]₂N⁺R³N⁺R⁵[R⁴(OR³)_y]₂(X⁻)₂

wherein the R², R³, R⁴, R⁵, y and X substituents are as defined above for the quaternary ammonium surfactants. These substituents are also preferably selected to provide diquaternary ammonium surfactants corresponding to the preferred quaternary ammonium surfactants. Particularly preferred are the C_8-16alkyl pentamethyl-ethylenediammonium chloride, bromide and methylsulfate salts.

Amine surfactants useful herein are of the formula:

[R²(OR³)_y][R⁴(OR³)_y]R⁵N

wherein the R², R³, R⁴, R⁵and y substituents are as defined above for the quaternary ammonium surfactants. Particularly preferred are the C₁₂-16 alkyl dimethyl amines.

Diamine surfactants herein are of the formula

[R²(OR³)_y][R⁴(OR³)_y]NR³NR⁵[R⁴(OR³)_y]

wherein the R², R³, R⁴, R⁵and y substituents are as defined above. Preferred are the C₁₂-C₁₆alkyl trimethylethylene diamines.

Amine oxide surfactants useful herein are of the formula:

[R²(OR³)_y][R⁴(OR³)_y]R⁵N→O

wherein the R², R³, R⁴, R⁵and y substituents are also as defined above for the quaternary ammonium surfactants. Particularly preferred are the C₁₂-16 alkyl dimethyl amine oxides.

Di(amine oxide) surfactants herein are of the formula:

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wherein the R², R³, R⁴, R⁵and y substituents are as defined above, preferably is C_12-16alkyl trimethylethylene di(amine oxide).

Other common cleaning adjuncts are identified in U.S. Pat. No. 7,326,675 and PCT Int. Publ. WO 99/05242. Such cleaning adjuncts are identified as including bleaches, bleach activators, suds boosters, dispersant polymers (e.g., from BASF Corp. or Dow Chemical) other than those described above, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, pigments, dyes, fillers, germicides, hydrotropes, anti-oxidants, enzyme stabilizing agents, pro-perfumes, carriers, processing aids, solvents, dye transfer inhibiting agents, brighteners, structure elasticizing agents, fabric softeners, anti-abrasion agents, and other fabric care agents, surface and skin care agents. Suitable examples of such other cleaning adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282, 6,306,812, 6,326,348 and PCT Int. Publ. WO99/05242, the teachings of which are incorporated herein by reference.

Fatty Acids

Similar to that disclosed in U.S. Pat. No. 4,561,998, the detergent compositions may contain a fatty acid containing from about 10 to about 22 carbon atoms. The fatty acid can also contain from about 1 to about 10 ethylene oxide units in the hydrocarbon chain. Suitable fatty acids are saturated and/or unsaturated and can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oils, grease, and mixtures thereof) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process). Examples of suitable saturated fatty acids for use in the detergent compositions include capric, lauric, myristic, palmitic, stearic, arachidic and behenic acid. Suitable unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid. Examples of preferred fatty acids are saturated C₁₀-C₁₄(coconut) fatty acids, from about 5:1 to about 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and mixtures of the above lauric/myristic blends with oleic acid at a weight ratio of about 4:1 to about 1:4 mixed lauric/myristic:oleic.

U.S. Pat. No. 4,507,219 identifies various sulfonate surfactants as suitable for use with the above-identified co-surfactants. The disclosures of U.S. Pat. Nos. 4,561,998 and 4,507,219 with respect to co-surfactants are incorporated herein by reference.

Softergents

Softergent technologies as described in, for example, U.S. Pat. Nos. 6,949,498, 5,466,394 and 5,622,925 can be used in the detergent compositions. “Softergent” refers to a softening detergent that can be dosed at the beginning of a wash cycle for the purpose of simultaneously cleaning and softening fabrics. The mid-chain headgroup or alkylene-bridged surfactants can be used to make stable, aqueous heavy duty liquid laundry detergent compositions containing a fabric-softening agent that provide exceptional cleaning as well as fabric softening and anti-static benefits.

Some suitable softergent compositions contain about 0.5% to about 10%, preferably from about 2% to about 7%, more preferably from about 3% to about 5% by weight of a quaternary ammonium fabric-softening agent having the formula:

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wherein R₁and R₂are individually selected from the group consisting of C₁-C₄alkyl, C₁-C₄hydroxy alkyl, benzyl, and —(C₂H₄O)_xH where x has a value from 2 to 5; X is an anion; and (1) R₃and R 4 are each a C₈-C₁₄alkyl or (2) R₃is a C₈-C₂₂alkyl and R₄is selected from the group consisting of C₁-C₁₀alkyl, C—C₁₀hydroxy alkyl, benzyl, and —(C₂H₄O)_xH where x has a value from 2 to 5.

Preferred fabric-softening agents are the mono-long chain alkyl quaternary ammonium surfactants wherein in the above formula R₁, R₂, and R₃are each methyl and R₄is a C₈-C₁₈alkyl. The most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C₈-C₁₆alkyl trimethyl ammonium salts, and C₈-C₁₆alkyl di(hydroxyethyl)-methyl ammonium salts. Of the above, lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride and coconut trimethylammonium chloride and methylsulfate are particularly preferred.

Another class of preferred quaternary ammonium surfactants are the di-C₈-C₁₄alkyl dimethyl ammonium chloride or methylsulfates; particularly preferred is di-C₁₂-C₁₄alkyl dimethyl ammonium chloride. This class of materials is particularly suited to providing antistatic benefits to fabrics.

A preferred softergent comprises the detergent composition wherein the weight ratio of anionic surfactant component to quaternary ammonium softening agent is from about 3:1 to about 40:1; a more preferred range is from about 5:1 to 20:1.

Odor Control

Odor control technologies as described in, for example, U.S. Pat. No. 6,878,695 can be used in the detergent compositions.

For example, a composition containing one or more of the mid-chain headgroup or alkylene-bridged surfactants can further comprise a low-degree of substitution cyclodextrin derivative and a perfume material. The cyclodextrin is preferably functionally-available cyclodextrin. The compositions can further comprise optional cyclodextrin-compatible and-incompatible materials, and other optional components. Such a composition can be used for capturing unwanted molecules in a variety of contexts, preferably to control malodors including controlling malodorous molecules on inanimate surfaces, such as fabrics, including carpets, and hard surfaces including countertops, dishes, floors, garbage cans, ceilings, walls, carpet padding, air filters, and the like, and animate surfaces, such as skin and hair.

The low-degree of substitution cyclodextrin derivatives useful herein are preferably selected from low-degree of substitution hydroxyalkyl cyclodextrin, low-degree of substitution alkylated cyclodextrin, and mixtures thereof. Preferred low-degree of substitution hydroxyalkyl beta-cyclodextrins have an average degree of substitution of less than about 5.0, more preferably less than about 4.5, and still more preferably less than about 4.0. Preferred low-degree of substitution alkylated cyclodextrins have an average degree of substitution of less than about 6.0, more preferably less than about 5.5, and still more preferably less than about 5.0.

The detergent compositions can comprise a mixture of cyclodextrins and derivatives thereof such that the mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivatives described hereinbefore. Such cyclodextrin mixtures preferably comprise high-degree of substitution cyclodextrin derivatives (having a higher average degree of substitution than the low-degree substitution cyclodextrin derivatives described herein) and non-derivatized cyclodextrin, such that the cyclodextrin mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivative. For example, a composition comprising a cyclodextrin mixture containing about 0.1% non-derivatized beta-cyclodextrin and about 0.4% hydroxypropyl beta-cyclodextrin having an average degree of substitution of about 5.5, exhibits an ability to capture unwanted molecules similar to that of a similar composition comprising low-degree of substitution hydroxypropyl beta-cyclodextrin having an average degree of substitution of about 3.3. Such cyclodextrin mixtures can typically absorb odors more broadly by complexing with a wider range of unwanted molecules, especially malodorous molecules, having a wider range of molecular sizes preferably at least a portion of a cyclodextrin mixture is alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin and its derivatives thereof, and/or beta-cyclodextrin and its derivatives thereof; more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin derivative, and derivatized beta-cyclodextrin, even more preferably a mixture of derivatised alpha-cyclodextrin and derivatized beta-cyclodextrin; and most preferably a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta-cyclodextrin, and/or a mixture of methylated alpha-cyclodextrin and methylated beta-cyclodextrin.

The cavities within the functionally-available cyclodextrin in the detergent compositions should remain essentially unfilled (i.e., the cyclodextrin remains uncomplexed and free) or filled with only weakly complexing materials when in solution, in order to allow the cyclodextrin to absorb (i.e., complex with) various unwanted molecules, such as malodor molecules, when the composition is applied to a surface containing the unwanted molecules. Non-derivatized (normal) beta-cyclodextrin can be present at a level up to its solubility limit of about 1.85% (about 1.85 g in 100 grams of water) at room temperature. Beta-cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit. Non-derivatized beta-cyclodextrin is generally not preferred when the composition contains surfactant since it affects the surface activity of most of the preferred surfactants that are compatible with the derivatized cyclodextrins.

The level of low-degree of substitution cyclodextrin derivatives that are functionally-available in the odor control compositions is typically at least about 0.001%, preferably at least about 0.01%, and more preferably at least about 0.1%, by weight of the detergent composition. The total level of cyclodextrin in the present composition will be at least equal to or greater than the level of functionally-available cyclodextrin. The level of functionally-available will typically be at least about 10%, preferably at least about 20%, and more preferably at least about 30%, by weight of the total level of cyclodextrin in the composition.

Concentrated compositions can also be used. When a concentrated product is used, i.e., when the total level of cyclodextrin used is from about 3% to about 60%, more preferably from about 5% to about 40%, by weight of the concentrated composition, it is preferable to dilute the concentrated composition before treating fabrics in order to avoid staining. Preferably, the concentrated cyclodextrin composition is diluted with about 50% to about 6000%, more preferably with about 75% to about 2000%, most preferably with about 100% to about 1000% by weight of the concentrated composition of water. The resulting diluted compositions have usage concentrations of total cyclodextrin and functionally-available cyclodextrin as discussed hereinbefore, e.g., of from about 0.1% to about 5%, by weight of the diluted composition of total cyclodextrin and usage concentrations of functionally-available cyclodextrin of at least about 0.001%, by weight of the diluted composition.

Forms

The detergent compositions can take any of a number of forms and any type of delivery system, such as ready-to-use, dilutable, wipes, or the like.

For example, the detergent compositions can be a dilutable fabric detergent, which may be an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried or dry-blended powder, a tablet, a paste, a molded solid, a water soluble sheet, or any other laundry detergent form known to those skilled in the art. A “dilutable” fabric detergent composition is defined, for the purposes of this disclosure, as a product intended to be used by being diluted with water or a non-aqueous solvent by a ratio of more than 100:1, to produce a liquor suitable for treating textiles. “Green concentrate” compositions like those on the market today for Fantastic®, Windex® and the like, can be formulated such that they could be a concentrate to be added to a bottle for final reconstitution.

The detergent compositions can also be formulated as a gel or a gel packet or pod like the dishwasher products on the market today. Water-soluble sheets, sachets, or pods such as those described in U.S. Pat. Appl. No. 2002/0187909, the teachings of which are incorporated herein by reference, are also envisaged as a suitable form. The detergent composition can also be deposited on a wiper or other substrate.

Polymeric Suds Enhancers

In some aspects, polymeric suds enhancers such as those described in U.S. Pat. No. 6,903,064 can be used in the detergent compositions. For example, the compositions may further comprise an effective amount of polymeric suds volume and suds duration enhancers. These polymeric materials provide enhanced suds volume and suds duration during cleaning.

Examples of polymeric suds stabilizers suitable for use in the compositions:

(i) a polymer comprising at least one monomeric unit having the formula:

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wherein each of R¹, R²and R³are independently selected from the group consisting of hydrogen, C₁to C₆alkyl, and mixtures thereof; L is O; Z is CH₂; z is an integer selected from about 2 to about 12; A is NR⁴R⁵, wherein each of R⁴and R⁵is independently selected from the group consisting of hydrogen, C₁to C₈alkyl, and mixtures thereof, or NR⁴R⁵form an heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by C₁to C₈hydrocarbyl;

(ii) a proteinaceous suds stabilizer having an isoelectric point from about 7 to about 11.5;

(iii) a zwitterionic polymeric suds stabilizer; or

(iv) mixtures thereof.

Preferably, the exemplary polymeric suds stabilizer described above has a molecular weight of from about 1,000 to about 2,000,000; more preferably the molecular weight is about 5,000 to about 1,000,000.

Methods of Laundering Fabrics

Methods for laundering fabrics with mid-chain headgroup or alkylene-bridged surfactant-based formulations are contemplated. Such methods involve placing fabric articles to be laundered in a high efficiency washing machine or a regular (non-high efficiency) washing machine and placing an amount of the detergent composition sufficient to provide a concentration of the composition in water of from about 0.001% to about 5% by weight when the machine is operated in a wash cycle. A high efficiency machine is defined by the Soap and Detergent Association as any machine that uses 20% to 66% of the water, and as little as 20%-50% of the energy, of a traditional, regular agitator washer (SDA “Washers and Detergents” publication 2005; see www.cleaning101.com). The wash cycle is actuated or started to launder the fabric articles. Hand washing using the inventive detergent compositions is also contemplated.

Thus, in one aspect, the invention is a method which comprises laundering one or more textile articles in water having a temperature less than 30° C., preferably from 5° C. to 30° C., the presence of an inventive detergent as described herein.

Other Applications

Although the mid-chain headgroup or alkylene-bridged surfactants have considerable value for laundry detergents, other end uses should benefit from their use. Thus, the surfactants should also be valuable in applications where greasy substances require removal or cleaning. Such applications include, for example, household cleaners, degreasers, sanitizers and disinfectants, light-duty liquid detergents, hard and soft surface cleaners for household, autodish detergents, rinse aids, laundry additives, carpet cleaners, spot treatments, softergents, liquid and sheet fabric softeners, industrial and institutional cleaners and degreasers, oven cleaners, car washes, transportation cleaners, drain cleaners, industrial cleaners, oil dispersants, foamers, defoamers, institutional cleaners, janitorial cleaners, glass cleaners, graffiti removers, adhesive removers, concrete cleaners, metal/machine parts cleaners, and food service cleaners, and other similar applications for which removal of greasy soils is advantageously accomplished, particularly at room temperature or below. The detergents may also be beneficial for certain personal care applications such as hand soaps and liquid cleansers, shampoos, and other hair/scalp cleansing products, especially for oily/greasy hair, scalp, and skin, which are also beneficial when effective with lukewarm or cold water.

The following examples merely illustrate the invention; those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

I. Preparation of Mid-Chain Headgroup Surfactants
9-Octadecanol

A 1-L flask containing magnesium turnings (13.3 g) is flame dried. A reflux condenser and an addition funnel, each fitted with a drying tube, are attached. A mechanical stirrer is also used, and all glassware is flame dried. Anhydrous tetrahydrofuran (THF, 100 mL) is added to the magnesium turnings. The addition funnel is charged with 1-bromononane (100.0 g) and dry THF (50 mL). The 1-bromononane solution is slowly added to the magnesium, and the reaction starts immediately. 1-Bromononane is added at a rate to keep the THF at reflux. After completing the alkyl halide addition, the reaction mixture stirs for an additional 30 min. Another addition funnel is charged with nonanal (68.7 g) and dry THF (50 mL). The nonanal solution is added as rapidly as possible while keeping the temperature at about 60° C. After completing the aldehyde addition, the reaction mixture stirs for an additional 30 min. at 60° C. After cooling, a stoichiometric amount of hydrochloric acid (25 wt. % aq. HCl) is added. Deionized water (50 mL) is added, and the THF layer is isolated and concentrated. 9-Octadecanol is purified using a column with neutral Brockman I alumina using 1:1 hexane:diethyl ether as an eluent. ¹H NMR analysis shows about 92% pure 9-octadecanol.

Sodium 9-octadecyl Sulfate

9-Octadecanol (64.9 g, 0.24 mol) is added to a 1-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (300 mL) is added, and the mixture is stirred. Sulfamic acid (24.4 g, 0.25 mol) and urea (5.0 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 14 h. ¹H NMR shows that the reaction is nearly complete. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 9-octadecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.6. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a column with Brockman I neutral alumina and 50:50 MeOH:deionized water as the eluent. The resulting mixture, which contains sodium 9-octadecyl sulfate, is stripped and analyzed (82.1% solids at 105° C., 99.3% actives by ¹H NMR).

8-Hexadecanol

A 3-L flask containing magnesium turnings (22.0 g) is flame dried. A reflux condenser and an addition funnel, each fitted with a drying tube, are attached. A mechanical stirrer is also used, and all glassware is flame dried. Anhydrous tetrahydrofuran (THF, 150 mL) is added to the magnesium turnings. The addition funnel is charged with 1-bromooctane (153.3 g) and dry THF (200 mL). The 1-bromooctane solution is slowly added to the magnesium, and the reaction starts immediately. 1-Bromooctane is added at a rate to keep the THF at reflux. After completing the alkyl halide addition, the reaction mixture stirs for an additional 45 min. Another addition funnel is charged with octanal (102.8 g) and dry THF (150 mL). The octanal solution is added as rapidly as possible while keeping the temperature at about 50° C. After completing the aldehyde addition, the reaction mixture stirs overnight. Ammonium chloride (43.9 g) is added to the beaker. Deionized water (300 mL) is added, and the THF layer is isolated and concentrated. 8-Hexadecanol is purified using methanol via recrystallization. ¹H NMR analysis shows about 96.5% pure 8-hexadecanol.

Sodium 8-hexadecyl Sulfate

8-Hexadecanol (67.9 g) is added to a 0.5 L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (400 mL) is added, and the mixture is stirred. Sulfamic acid (28.0 g) and urea (6.7 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 7.5 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 8-hexadecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting aqueous mixture, which contains sodium 8-hexadecyl sulfate, is stripped and analyzed (97.4% actives by ¹H NMR).

2-(Octadecan-9-yloxy)ethanol and 2-(2-(2-(octadecan-9-yloxy)ethoxy)-ethoxy)ethanol

9-Octadecanol (2102.7 g) and 45% KOH (18 g) are charged to a 316 stainless steel pressure reactor. The reactor is sealed and heated to 100° C. to remove excess water for 2 h at 30 mm Hg. Afterwards, the vacuum is broken with the addition of nitrogen. The reactor is heated to 145-160° C. and nitrogen is added prior to ethylene oxide (EO) addition. EO is added at 145-160° C. to reach the desired 1 and 3 moles of EO per mole of 9-octadecanol. The temperature is held at 145-160° C. for 1 h or until pressure equilibrates. The reactor is cooled and the desired product is removed. Gel permeation chromatography (GPC) is used to characterize the reaction product, which contains 38.4% of ethoxylated alcohols and 61.6% free 9-octadecanol for the 1 mole EO material and 59.1% of ethoxylated alcohols and 40.9% of free 9-octadecanol for the 3 mole EO material.

Sodium 2-(octadecan-9-yloxy)ethyl sulfate

2-(Octadecan-9-yloxy)ethanol (70 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (200 mL) is added, and the mixture is stirred. Sulfamic acid (22.5 g) and urea (0.25 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 8 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-(octadecan-9-yloxy)ethyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting aqueous mixture, which contains sodium 2-(octadecan-9-yloxy)ethyl sulfate, is stripped and analyzed (93.0% actives by ¹H NMR).

Sodium 2-(2-(2-(octadecan-9-yloxy)ethoxy)ethoxy)ethyl sulfate

2-(2-(2-(Octadecan-9-yloxy)ethoxy)ethoxy)ethanol (50 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (250 mL) is added, and the mixture is stirred. Sulfamic acid (12.4 g) and urea (3.0 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 16 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-(2-(2-(octadecan-9-yloxy)ethoxy)ethoxy)ethyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting aqueous mixture, which contains sodium 2-(2-(2-(octadecan-9-yloxy)ethoxy)ethoxy)ethyl sulfate, is stripped and analyzed (97.1% actives by ¹H NMR).

9-Octadecene

1-Decene (371 g, 2.65 mol) and activated alumina (37.1 g, activated by heating at 120° C. for 4 h) are combined in an Erlenmeyer flask and stirred at room temperature overnight with a drying tube attached. The mixture is filtered under vacuum to remove alumina. The 1-decene is transferred to a flask equipped with condenser, rubber septum, nitrogen inlet needle, thermocouple, heating mantle, magnetic stirring, and an outlet from the condenser outlet to a vegetable oil bubbler to monitor ethylene production. The mixture is sparged with nitrogen during heating to 60° C. and then sparged for another 30 minutes. Metathesis catalyst (“RF3,” a ruthenium-based catalyst supplied by Evonik, 117 mg, 0.132 mmol) is then added via a funnel weigh boat. Ethylene production occurs as indicated by faint foaming in the reaction mixture and bubbler activity when the nitrogen pad is briefly turned off. The reaction mixture is filtered through Celite 545 filter aid and then used for sulfonation. Reaction time: 24 h. Proton NMR indicates a complete absence of terminal vinyl protons.

Sulfonation of 9-octadecene

Chlorosulfonic acid (23.35 g, 0.200 mol) is added dropwise to a solution of 9-octadecene (50.00 g, 0.196 mol) in chloroform (250 mL) at 6° C. in a 500-mL flask over 45 min., and the ice-cooled mixture is allowed to stir for 1 h. Chloroform is removed at 29° C., ultimately at 20 mbar. Thereafter, the product is placed in a dropping funnel and added with mechanical stirring to aqueous sodium hydroxide (29.15 g of 33% NaOH solution, 1.2 eq. based on chlorosulfonic acid) that is pre-chilled while maintaining the temperature below 7° C. The mixture is heated gently to 32° C. for 2 h, and then at 92° C. overnight. The product is allowed to cool in a graduated cylinder and diluted with an additional 117.15 g of water to provide a cloudy, pale yellow dispersion with about 35% actives.

Addition of ethylene glycol n-butyl ether (BEE, 15 pph) and Ninol® 201 (10 pph; 70% N,N-diethanol oleamide, 23% diethanol amine, 7% water) to the final product provides a nearly transparent product, which is sodium 9-octadecenyl sulfonate (28% actives). Ninol® 201 content: 8.0%; BEE: 12.0%.

9-Bromooctadecane

9-Octadecene (400 mL) is placed in a 3-neck, 1-L flask equipped with an ice bath, a hydrogen bromide gas inlet with bubbler, magnetic stirring, an outlet tube leading to a trap, caustic scrubber, and a valved outlet tube. Hydrogen bromide is added over 6 h, and disappearance of signals from olefinic protons is verified by ¹H NMR. Nitrogen is added to the flask to purge remaining HBr for 3 h. ¹H NMR shows 97.2% actives.

N,N′-Dimethyloctadecan-9-amine

9-Bromooctadecane is added to a Parr reactor where it is treated with neat dimethylamine. The resulting crude N,N′-dimethyloctadecan-9-amine is purified via distillation. ¹H NMR analysis shows about 97.9% pure N,N′-dimethyloctadecan-9-amine.

Betaine of N,N′-dimethyloctadecan-9-amine

Deionized water (29.5 g) is added to a 500-mL, 4-neck, flask along with sodium 2-chloroacetate (13.3 g) and isopropyl alcohol (190 g). N,N-Dimethyloctadecan-9-amine (35.1 g) is slowly added to the flask. The flask is sealed under nitrogen and heated to 75° C. The reaction mixture stirs for 43 h. The solvent is removed by rotary evaporation, and the product is purified to give the desired betaine.

10-Icosanol

The procedure described for the preparation of 9-octadecanol is generally followed using 1-bromodecane and decanal as starting materials. The resulting 10-icosanol gives satisfactory analytical results.

Sodium 10-icosanyl Sulfate

The procedure described for the preparation of 9-octadecyl sulfate is generally followed except that 10-icosanol is used instead of 9-octadecanol. The resulting alcohol sulfate gives satisfactory analytical results.

22-Methyltetracosan-11-ol
2-((11-Bromoundecyl)oxy)tetrahydro-2H-pyran

A 2000-mL, 4-neck flask outfitted with mechanical stirrer, thermocouple, reflux condenser and N₂purge is charged with diethyl ether (800 g). The 11-bromoundecan-1-ol (100.0 g) is added in one portion and stirring is started. p-Toluenesulfonic acid (1.0 g) is added followed by 3,4-dihydro-2H-pyran (66.7 g, about 2 eq.), and the mixture is stirred under N2 overnight. The mixture is transferred to a 2000-mL separatory funnel and extracted with a saturated solution of sodium bicarbonate. The mixture is filtered through a plug of silica. GPC shows ˜99% yield of the desired product.

2-((12-Methyltetradecyl)oxy)tetrahydro-2H-pyran

Two separate reactors are used in this coupling step. First, magnesium (17 g, ˜1.1 eq.) is added to a 1000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel and N₂purge. The set-up is flame dried and drying tubes are added to the addition funnel and reflux condenser. Anhydrous THF (150 g) is added to the flask. 2-Bromobutane (85 g) and THF (100 g) are added to the addition funnel. The contents from the addition funnel are slowly added to the flask. Once the reaction is underway, the temperature is kept at about 60° C. Once the addition of the 2-bromobutane is complete, the reaction mixture is stirred for an additional 0.5 h while maintaining the temperature at about 50° C.

Anhydrous THF (300 g) is charged to a separate 4-neck, 3000-mL flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and N2 purge, and the solvent is cooled to about −50° C. with a dry ice/isopropanol bath. Copper(II) chloride (9.2 g, 0.17 eq.) and lithium chloride (5.6 g, 0.33 eq.) are added to the reaction flask. Next, 2-((11-bromoundecyl)oxy)tetrahydro-2H-pyran (133.9 g, 1.0 eq.) is added. The Grignard reagent from the previous step, bromo(sec-butyl)magnesium (100 g, ˜1.5 eq.), is added to the addition funnel and dripped slowly into the second reaction flask. The temperature is kept at or below −40° C. while dripping in the Grignard reagent. After the addition is complete, the mixture is allowed to warm to room temperature and is then stirred overnight. Saturated aqueous ammonium chloride is added, the mixture is stirred for about 15 min., and the organic layer is isolated. The water layer is washed once with hexane. The organic layers are combined and filtered through florisil, then through silica, and concentrated. Gel permeation chromotography shows 88% of the desired product.

12-Methyltetradecan-1-ol

2-((12-Methyltetradecyl)oxy)tetrahydro-2H-pyran (113.4 g) is added to a 1000-mL, 4-neck flask equipped with reflux condenser, thermocouple, and mechanical stirrer. Methanol (500 g) and 25% aq. HCl (3.8 g) and p-toluenesulfonic acid (14 g) are added to the flask. The mixture is stirred under reflux for 48 h. The reaction mixture is added to saturated sodium bicarbonate solution, and the product is filtered through a plug of silica. Methanol and water are stripped, and the concentrated product is recrystallized from methanol. ¹H NMR (CDCl₃) indicates a quantitative yield of the desired alcohol.

12-Methyltetradecanal

Dichloromethane (1080 g) is added to a 2000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel and N₂purge. Molecular sieves (3 A, 250 g) are added to the flask along with pyridinium chlorochromate (187 g, 2.5 eq.). 12-Methyltetradecan-1-ol (77.7 g) is slowly added. After the addition is complete, the mixture is stirred for 1 h. The product is filtered through florisil, and the residue is washed with dichloromethane. The product is then concentrated. FT-IR shows a carbonyl peak at about 1710 cm⁻¹and no evidence of alcohol impurities.

22-Methyltetracosan-11-ol

Magnesium (5.3 g, 1.1 eq.) is added to a 2000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel and N2 purge. The apparatus is flame dried and drying tubes are added to the addition funnel and reflux condenser. Anhydrous THF (200 g) is added to the flask. 1-Bromodecane (42 g) and THF (50 g) are charged to the addition funnel and then added slowly to the reaction flask. Once the reaction is underway, the temperature of the reaction mixture is kept at about 60° C. When the addition of the 1-bromodecane is complete, the reaction mixture is stirred for an additional 15 min.

12-Methyltetradecanal (42 g) and anhydrous THF (50 g) are added to the addition funnel and then added slowly to the previously made decylmagnesium bromide (46.6 g, ˜1 eq.). The reaction temperature is kept at about 55° C. throughout the addition. Once the 12-methyltetradecanal addition is complete, the mixture is stirred for an additional 30 min. Saturated ammonium chloride solution is then added. The resulting solution is separated, and the organic layer is concentrated. The crude alcohol is recrystallized four times from hexane. The ¹H NMR shows a 92% yield of the desired product, 22-methyltetracosan-11-ol.

Sodium 22-methyltetracosan-11-yl sulfate

22-Methyltetracosan-11-ol (21 g) is added to a 500-mL, 4-neck flask equipped with mechanical stirrer, reflux condenser, thermocouple, and N₂purge. 1,4-Dioxane (300 g), urea (2.5 g, 0.7 eq.), and sulfamic acid (9.7 g, 1.8 eq.) are added to the flask. The mixture is stirred for 24 h at reflux. The mixture is concentrated, and the resulting sulfate is dissolved in MeOH. The pH is adjusted to about 10 with 50% NaOH. Methanol is then stripped. The concentrated sulfate salt is dissolved in a 50:50 water:ethanol solution and is extracted twice with petroleum ether. The water:ethanol layer is concentrated, and the product is dried. ¹H NMR shows quantitative conversion to the desired alcohol sulfate.

12-Methyltetradecan-6-ol
2-((5-Bromopentyl)oxy)tetrahydro-2H-pyran

A 1000-mL, 4-neck flask outfitted with mechanical stirrer, thermocouple, N₂purge, and reflux condenser is charged with diethyl ether (1200 g). 5-Bromopentan-1-ol (200.0 g) is added in one portion and stirring is started. p-Toluenesulfonic acid (1.2 g) is added followed by 3,4-dihydro-2H-pyran (268 g, 2.7 eq.). The mixture is stirred under N₂overnight, then transferred to a 2000-mL separatory funnel and extracted with saturated aqueous sodium bicarbonate. The mixture is purified using a silica column with 9:1 hexane:methyl t-butyl ether as the mobile phase. The solvent is stripped, and the product is dried with magnesium sulfate. Gel permeation chromotography indicates ˜94% of the desired product.

2-((7-Methylnonyl)oxy)tetrahydro-2H-pyran

Two separate reactors are used in this coupling step. First, magnesium (21.1 g, 0.75 eq.) is added to a 1000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel and N₂purge. The apparatus is flame dried and drying tubes are added to the addition funnel and reflux condenser. Anhydrous THF (100 g) is added. 1-Bromo-2-methylbutane (175 g) and THF (150 g) are charged to the addition funnel, and the mixture is slowly added to the reaction flask. Once the reaction is underway, the temperature of the reaction mixture is kept at ˜60° C. When the addition of the 1-bromo-2-methylbutane is complete, the mixture is stirred for an additional 15 min.

A separate 4-neck 3000-mL flask equipped with a mechanical stirrer, reflux condenser, thermocouple, and N₂purge is charged with anhydrous THF (250 g). The solvent is cooled to −50° C. with a dry ice/isopropanol bath. Copper(II) chloride (17.1 g, 0.17 eq.) and lithium chloride (10.8 g, 0.34 eq.) are added to the reaction flask. Next, 2-((5-bromopentyl)oxy)tetrahydro-2H-pyran (185.9 g, 1.0 eq.) is added. The Grignard reagent from the previous step, bromo(2-methylbutyl)magnesium (203 g, 1.56 eq.), is added slowly from the addition funnel. The temperature is kept at or below −50° C. while adding the Grignard reagent. After the addition is complete, the mixture is allowed to warm to room temperature, and is stirred overnight. Saturated aqueous ammonium chloride solution is added and stirred for 15 min. The resulting solution is placed in a separatory funnel and the organic layer is isolated. The water layer is washed with hexane and separated. The combined organic layers are filtered through silica and concentrated. Gel permeation chromotography shows 91% of the desired product.

7-Methylnonan-1-ol

2-((7-Methylnonyl)oxy)tetrahydro-2H-pyran (183 g) is added to a 3000-mL, 4-neck flask equipped with reflux condenser, thermocouple, and mechanical stirrer. Methanol (1500 g) and 25% aqueous HCl (38 g) are added to the flask. The mixture is stirred under reflux for 24 h. Methanol is stripped, and the product is distilled. ¹H NMR shows 89% of the desired alcohol.

7-Methylnonanal

Dichloromethane (1300 g) is added to a 2000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel, and N₂purge. Molecular sieves (3A, 250 g) are added to the flask along with pyridinium chlorochromate (222.3 g, 2.5 eq.). 7-Methylnonan-1-ol (64 g) is slowly added. After the addition is complete, the reaction mixture is stirred for 1 h. The product is filtered through florisil and the residue is washed twice with dichloromethane. The dichloromethane is then stripped. FT-IR shows a carbonyl peak at ca. 1710 cm⁻¹and no evidence of alcohol impurities. The product is filtered again through florisil and dried (MgSO4) prior to use in the next step.

12-Methyltetradecan-6-ol

Magnesium (3.55 g, 1.13 eq.) is added to a 1000-mL, 4-neck flask equipped with a mechanical stirrer, thermocouple, reflux condenser, addition funnel, and N₂purge. The apparatus is flame dried and drying tubes are added to the addition funnel and reflux condenser. Anhydrous THF (100 g) is added to the flask. 1-Bromopentane (19.5 g) and THF (25 g) are charged to the addition funnel and added slowly to the reaction flask. Once the reaction is underway, the temperature of the mixture is kept at ca. 40° C. When the 1-bromopentane addition is complete, the mixture is stirred for an additional 30 min.

7-Methylnonanal (20.5 g) and anhydrous THF (25 g) are charged to the addition funnel and added slowly to the previously made bromo(pentyl)magnesium (22.6 g, ˜1 eq.). The reaction temperature is kept at ca. 35° C. throughout the addition. When the 7-methylnonanal addition is complete the mixture is stirred for an additional 30 min. A solution of 25% HCl (18.7 g, 1 eq.) is diluted with water (250 g), and this mixture is added to the reaction mixture. The resulting mixture is separated and the organic layer is concentrated. ¹H NMR shows a 94% yield of the desired product.

Sodium 12-methyltetradecan-6-yl Sulfate

12-Methyltetradecan-6-ol (26 g) is added to a 1000-mL, 4-neck flask equipped with mechanical stirrer, reflux condenser, thermocouple, and N₂purge. 1,4-Dioxane (500 g), urea (1.6 g, 0.2 eq.), and sulfamic acid (11.4 g, 1.03 eq.) are added to the flask. The mixture is stirred for 4 h at reflux. The 1,4-dioxane is stripped, and the resulting sulfate is dissolved in MeOH. The pH is adjusted to about 10 with 50% NaOH. The MeOH is stripped, and the product is passed through a silica column using 8:1 methylene chloride:MeOH. ¹H NMR indicates a 90% yield of the desired product.

Dynamic Contact Angle of Surfactant Solutions on Beef Tallow Cotton Swatches

Table 1 shows results of measuring the dynamic contact angle of a 0.1 wt. %

actives surfactant solution on cotton swatches treated with beef tallow greasy soil. Both the surfactant solution and the beef tallow-containing swatch are cooled to 60° F. The results in Table 1 indicate that when used alone, both sodium 9-octadecyl sulfate and sodium 10-icosanyl sulfate wet the surface of a beef tallow swatch better than the conventional surfactants Na AES (fatty alcohol ethoxylate sulfate, sodium salt), Na LAS (linear alkylbenzene sulfonate, sodium salt), and SLS (sodium lauryl sulfate). In addition, once coupled with Neodol® 25-7 (fatty alcohol ethoxylate) at 3:1 anionic to nonionic % active ratio, the sodium 9-octadecyl sulfate still has a much lower wetting time on beef tallow and outperforms the other surfactants. Interestingly, each of the other control surfactants, when combined with Neodol® 25-7, gives the same dynamic contact angle results, suggesting that Neodol® 25-7 overpowers the control anionic surfactants in terms of its ability to wet beef tallow soil. This is not the case, however, for sodium 9-octadecyl sulfate or for sodium 10-icosanyl sulfate.

TABLE 1

Dynamic Contact Angle of Surfactant Solutions on Beef Tallow

Cotton Swatches

Initial
Time
Time to

Advancing
for 90%
Reach

Contact
Droplet
2° Contact

Angle
Sorption
Angle

Ex.
Surfactant (0.1 wt. % actives)
(°)
(s)
(s)

C1
Na AES
72.2
1130
1500+

C2
Na LAS/Neodol ® 25-7
63.6
604
942

C3
SLS/Neodol ® 25-7
64.1
600
923

C4
Na AES/Neodol ® 25-7
63.6
559
916

C5
Na LAS
58.8
376
575

6
Sodium 9-octadecyl sulfate/
55.0
240
354

Neodol ® 25-7

7
Sodium 9-octadecyl sulfate
44.0
130
178

8
Sodium 10-icosanyl sulfate
40.1
98.5
135.5

Na AES = sodium C₁₂-C₁₄alcohol ethoxylate (3 EO) sulfate (Steol ® CS-330);

Na LAS = linear sodium alkylbenzene sulfonate (Bio-Soft ® S-101);

SLS = sodium C₁₂-C₁₄alcohol sulfate (Stepanol ® WA-Extra), products of Stepan Company;

Neodol ® 25-7 = C₁₂-C₁₅7EO ethoxylate, product of Shell.

Procedure for Testing Laundry Detergent Samples

Laundry detergent (to give 0.1% actives in washing solution) is charged to the washing machine, followed by soiled/stained cotton fabric swatches that are attached to pillowcases. The following standard soiled/stained fabric swatches are used: bacon grease, butter, cooked beef fat, and beef tallow. At least three of each kind of swatch are used per wash. Swatches are stapled to pillowcases for laundering, and extra pillowcases are included to complete a six-pound load. Wash temperature: 60° F. Rinse temperature: 60° F. Wash cycles are 30 min in front-loading high-efficiency washing machines. The swatches are detached from pillowcases, dried, and ironed. The same procedure is used to launder all of the pillowcases/swatches, with care taken to ensure that water temperature, wash time, manner of addition, etc. are held constant for the cold-water wash process. When the cycle is complete, swatches are removed from the pillowcases, dried at low heat on a rack, and pressed gently and briefly with a dry iron.

Swatches are scanned to measure the L*a*b* values, which are used to calculate a soil removal index (SRI) for each type of swatch. Finally, the ΔSRI is calculated, which equals the experimental sample SRI minus the SRI of a pre-determined standard laundry detergent formula (or control). When |ΔSRI|≥0.5 differences are perceivable to the naked eye. If the value of ΔSRI is greater than or equal to 0.5, the sample is superior. If ΔSRI is less than or equal to −0.5, the sample is inferior. If ΔSRI is greater than −0.5 and less than 0.5, the sample is considered equal to the standard.

A Hunter LabScan® XE spectrophotometer is used to determine the L*a*b* values to calculate the SRI for every type of swatch, and the stain removal index (SRI) is calculated as follows:

$SRI = 100 - \sqrt{{(L_{clean}^{*} - L_{washed}^{*})}^{2} + {(a_{clean}^{*} - a_{washed}^{*})}^{2} + {(b_{clean}^{*} - b_{washed}^{*})}^{2}}$

$Δ SRI = {SRI}_{sample} - {SRI}_{standard}$

II. Performance of Mid-Chain Headgroup Surfactants in Cold-Water Cleaning

Performance results for cold-water cleaning are compared. The target performance (which corresponds to a ΔSRI value of 0.0) is that of a commercial cold-water detergent or a control cold-water detergent used with a cold-water wash (60° F.) and cold-water rinse (60° F.).

As a practical matter, the improvement in wetting ability of beef tallow soil observed with sodium 9-octadecyl sulfate (or sodium 10-icosanyl sulfate) shown in Table 1 is helpful if it translates to an improvement in cold-water cleaning performance.

Table 2 provides details for formulations in which a leading cold-water detergent is reformulated to replace one of the two anionic surfactants normally present with sodium 9-octadecyl sulfate. For example, in Formulation A, sodium 9-octadecyl sulfate replaces a sodium C₁₂-C₁₄alcohol ethoxylate (3 EO) sulfate (Na AES) in the cold-water laundry detergent, while in Formulation B, sodium 9-octadecyl sulfate replaces a linear sodium alkylbenzene sulfonate (Na LAS) component.

As Table 3 shows, replacement of the Na LAS or Na AES in the control cold-water high-efficiency detergent with sodium 9-octadecyl sulfate, sodium 8-hexadecyl sulfate, or sodium 2-(octadecan-9-yloxy)ethyl sulfate as the mid-chain headgroup surfactant gives a remarkable improvement in cleaning greasy soils such as bacon grease, beef tallow, or cooked beef fat compared with the control formulations.

TABLE 2

Cold-Water Liquid Laundry Detergent Formulations

Formulation (wt. %)

Control
A
B
C
D
E

Sodium citrate dihydrate
3.5
3.5
3.5
3.5
3.5
3.5

Biosoft ® S-101 (97.4%), HLAS
8.1
8.1
—
8.1
—
8.1

NaOH (50%)
2.0
1.0
—
2.0
—
1.0

Monoethanolamine, 99%
2.1
2.1
2.1
2.1
2.1
2.1

Neodol ® 25-7, 100%
11.9
11.9
11.9
11.9
11.9
11.9

Stepanate ® SCS (44.9%) (Na
2.5
2.5
2.5
2.5
2.5
2.5

cumene sulfonate)

Coco fatty acid, Emry 622
2.95
2.95
2.95
2.95
2.95
2.95

(100%)

Sodium C₁₂-C₁₄alcohol
7.74
—
7.74
—
7.74
—

ethoxylate (3 EO) sulfate

(100%), Na AES

Sodium 9-octadecyl sulfate
—
8.10
8.30
—
—
—

(95.3%)

Sodium 8-hexadecyl sulfate
—
—
—
8.10
8.28
—

(95.6%)

Sodium 2-(octadecan-9-
—
—
—
—
—
8.10

yloxy)ethyl sulfate (95.4%)

Deionized water
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%

adjusted pH
8.8
8.5
8.6
8.8
8.5
8.5

TABLE 3

Detergency Performance in Cold-Water Cleaning: Greasy Soils

ΔSRI of Cleaning Data at

60° F. wash/60° F. rinse

Test formulation (0.1%
Bacon

Cooked Beef
Beef

actives)
Grease
Butter
Fat
Tallow

Na LAS/Na AES (3 EO)/
0.0
0.0
0.0
0.0

Neodol ® 25-7 (control)

Sodium 9-octadecyl
3.25
0.36
2.33
8.86

sulfate/Na LAS/

Neodol ® 25-7

(Formulation A)

Sodium 9-octadecyl
3.21
0.57
3.77
6.73

sulfate/Na AES (3 EO)/

Neodol ® 25-7

(Formulation B)

Sodium 8-hexadecyl
2.58
0.18
4.19
12.28

sulfate/Na LAS/

Neodol ® 25-7

(Formulation C)

Sodium 8-hexadecyl
2.57
0.21
0.85
8.10

sulfate/Na AES (3 EO)/

Neodol ® 25-7

(Formulation D)

Sodium 2-(octadecan-9-
4.06
0.76
1.54
11.45

yloxy)ethyl sulfate/Na LAS/

Neodol ® 25-7

(Formulation E)

III. Preparation of Alkylene-Bridged Surfactants
Sodium 2-hexyl-1-decyl Sulfate

2-Hexyl-1-decanol (100.3 g) is added to a 1-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (500 mL) is added, and the mixture is stirred. Sulfamic acid (42.7 g) and urea (10.2 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 7 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-hexyl-1-decyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting mixture, which contains sodium 2-hexyl-1-decyl sulfate, is stripped and analyzed (96.9% actives by ¹H NMR).

Sodium 2-octyl-1-decyl Sulfate/Sodium 2-hexyl-1-dodecyl Sulfate

2-Octyl-1-decanol/2-hexyl-1-dodecanol (199.6 g) is added to a 1-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (400 mL) is added, and the mixture is stirred. Sulfamic acid (62.2 g) and urea (15.4 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 6.5 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-octyl-1-decyl/2-hexyl-1-dodecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.4. Methanol is removed. ¹H NMR analysis shows significant impurities. The product is purified using a separatory funnel and 50:50 EtOH:deionized water with petroleum ether as extractant. The resulting mixture, which contains sodium 2-octyl-1-decyl sulfate/sodium 2-hexyl-1-dodecyl sulfate, is stripped and analyzed (98.5% actives by ¹H NMR).

Sodium 2-octyl-1-dodecyl Sulfate

2-Octyl-1-dodecanol (80.0 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (240 mL) is added, and the mixture is stirred. Sulfamic acid (27.6 g) and urea (3.2 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 21 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-octyl-1-dodecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.0. The resulting mixture, which contains sodium 2-octyl-1-dodecyl sulfate, is stripped and analyzed (96.1% actives by ¹H NMR).

Sodium 2-hexyl-1-nonyl Sulfate
N-Octylidene-cyclohexanamine

A 1-L flask outfitted with mechanical stirrer, reflux condenser with N₂inlet, and addition funnel is charged with hexanes (200 mL), molecular sieves (20 g), and octanal (100.0 g). Cyclohexylamine (154.9 g) is added slowly via the addition funnel to the stirring solution over 30 min. The reaction stirs at room temperature overnight. The reaction mixture is vacuum filtered over Celite® filter aid (Imerys Minerals) and is concentrated by rotary evaporation. The crude product is combined with hexanes (250 mL), then washed with water (4×250 mL) and brine (2×250 mL). The organic phase is dried (MgSO₄), filtered, and concentrated.

2-Hexyl-1-nonanal

A 3-L flask outfitted with thermocouple, mechanical stirrer, and nitrogen inlet is charged with N-octylidene-cyclohexanamine (77.6 g) and THF (580 mL). The reaction mixture is cooled in an isopropanol/dry ice bath. An addition funnel containing 2 M lithium diisopropylamide (LDA) in THF/heptane/ethylbenzene (225 mL) is introduced. The LDA solution is added slowly to the stirring reaction mixture. Additional THF (20 mL) is used to rinse the addition funnel. The dry ice/IPA bath is replaced with an ice water bath and the solution warms to 0° C. The addition funnel is replaced with another one charged with 1-bromoheptane (76.3 g). The 1-bromoheptane is added dropwise to the reaction mixture while keeping the reaction temperature below 10° C. The reaction mixture warms slowly to room temperature overnight. The mixture is cooled using an ice water bath. Hydrochloric acid (50 mL of 1 N solution) is added dropwise to the mixture to quench any remaining LDA. When all of the 1 N HCl has been added, 4 N HCl (300 mL) is added. The reaction mixture is transferred to a separatory funnel and the layers are separated. The aqueous phase is extracted with hexanes. The organic layers are combined and washed with water (5×500 mL) and brine (500 mL). The organic phase is dried (MgSO₄), filtered, and concentrated.

2-Hexyl-1-nonanol

A 3-L flask equipped with thermocouple, mechanical stirrer, reflux condenser with nitrogen inlet, and rubber septum is charged with crude 2-hexyl-1-nonanal (87.2 g) and ethanol (115 mL). The solution is cooled using an ice water bath. Sodium borohydride (18.2 g) is added slowly. The mixture warms slowly to room temperature and is left to react overnight. The reaction mixture is filtered through Celite® filter aid to obtain a clear yellow solution. A significant amount of solid is collected, and washed with ethanol. The filtrate is partitioned with a mixture of water and hexanes. The aqueous layer is removed and the organic layer is washed with water (5×300 mL) and brine (300 mL). The organic phase is dried (MgSO₄), filtered, and concentrated. The crude alcohol product is purified by short-path distillation prior to sulfation.

Sodium 2-hexyl-1-nonyl Sulfate

2-Hexyl-1-nonanol (41.5 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (300 mL) is added, and the mixture is stirred. Sulfamic acid (18.2 g) and urea (0.46 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 7 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-hexyl-1-nonyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10. The resulting mixture, which contains sodium 2-hexyl-1-nonyl sulfate, is stripped and analyzed (94% actives by ¹H NMR).

Sodium 2-heptyl-1-decyl Sulfate
N-Nonylidene-Cyclohexanamine

A 1-L flask outfitted with mechanical stirrer, reflux condenser with N₂inlet, and addition funnel is charged with hexanes (200 mL), molecular sieves (20 g), and nonanal (102.1 g). Cyclohexylamine (140.5 g) is added slowly via the addition funnel to the stirring solution over 30 min. The reaction stirs at room temperature overnight. ¹H NMR analysis of a sample shows that the reaction is complete. The reaction mixture is vacuum filtered over Celite® filter aid and is concentrated by rotary evaporation at 45° C. Excess cylohexylamine is removed under high vacuum by short-path distillation to provide the desired product.

2-Heptyl-1-decanal

A 3-L flask outfitted with thermocouple, mechanical stirrer, and nitrogen inlet is charged with N-nonylidene-cyclohexanamine (158.4 g) and THF (530 mL). The reaction mixture is cooled in an isopropanol/dry ice bath. An addition funnel containing 2 M lithium diisopropylamide (LDA) in THF/heptane/ethylbenzene (375 mL) is introduced. The LDA solution is added slowly to the stirring reaction mixture. Additional THF (20 mL) is used to rinse the addition funnel. The dry ice/IPA bath is replaced with an ice water bath and the solution warms to 0° C. The addition funnel is replaced with another one charged with 1-bromooctane (144.3 g). The 1-bromooctane is added dropwise to the reaction mixture while keeping the reaction temperature below 10° C. The reaction mixture warms slowly to room temperature overnight. ¹H NMR analysis indicates that the reaction is complete. The mixture is cooled using an ice water bath. Hydrochloric acid (120 mL of 1 N solution) is added dropwise to the mixture to quench any remaining LDA. When all of the 1 N HCl has been added (pH >11), 3 N HCl (350 mL) is added until the pH reaches ˜3. The ice bath is removed, and the solution stirs at room temperature. The reaction mixture is transferred to a separatory funnel and the layers are separated. The aqueous phase is extracted with diethyl ether (2×400 mL). The organic layers are combined and washed with water (4×600 mL) and brine (2×500 mL). The organic phase is dried (MgSO₄), filtered, and concentrated (rotary evaporation; then high vacuum).

2-Heptyl-1-decanol

A 3-L flask equipped with thermocouple, mechanical stirrer, reflux condenser with nitrogen inlet, and rubber septum is charged with crude 2-heptyl-1-decanal (207.3 g) and ethanol (410 mL). The solution is cooled using an ice water bath. Sodium borohydride (57.5 g) is added slowly. The mixture warms slowly to room temperature and is left to react over the weekend. The reaction mixture is filtered through Celite® filter aid to obtain a clear yellow solution. A significant amount of solid is collected, and washed with ethanol. The filtrate is partitioned with a mixture of water and hexanes. The aqueous layer is removed and the organic layer is washed with water (3×500 mL) and brine (500 mL). The organic phase is dried (MgSO₄), filtered, and concentrated. The crude product is purified by short-path distillation prior to sulfation.

Sodium 2-heptyl-1-decyl Sulfate

2-Heptyl-1-decanol (33.8 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (400 mL) is added, and the mixture is stirred. Sulfamic acid (13.5 g) and urea (3.26 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 6 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-heptyl-1-decyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10. The resulting mixture, which contains sodium 2-heptyl-1-decyl sulfate, is stripped and analyzed (94% actives by ¹H NMR).

Sodium 2-octyl-1-undecyl Sulfate
N-Decylidene-Cyclohexanamine

A round-bottom flask equipped with a magnetic stir bar is charged with hexanes (200 mL), cyclohexylamine (150 mL), and 3 A molecular sieves (20 g). The mixture is stirred at room temperature. Decanal (120 mL) is added, and the mixture is stirred at room temperature for 65 h. Analysis by ¹H NMR confirms that conversion to the desired imine is complete. The crude product is filtered and concentrated by rotary evaporation at 35° C., then further stripped under high vacuum at room temperature.

2-Octyl-1-undecanal

N-Decylidene-cyclohexanamine (126.7 g, 0.534 mol) and THF (400 mL) are charged to a 3-L round-bottom flask equipped with N₂inlet, overhead stirrer, and an addition funnel. The stirred mixture is cooled to −77° C. using a dry ice/isopropanol bath. Lithium diisopropylamide (275 mL of 2 M solution in THF/heptane/ethylbenzene, 0.550 mol) is added over 45 min. to the stirred solution. The mixture stirs at −77° C. for an additional 10 min. and then warms to 0° C. in an ice water bath. After 0.5 h, 1-bromononane (105 mL) is added over 30 min. The mixture is stirred at 0° C. for an additional hour, the ice water bath is removed, and the solution warms slowly to room temperature. After stirring at room temperature for 16 h, the mixture is cooled to 0° C. and quenched with 1 N HCl (100 mL). Hydrochloric acid (2 N) is added to achieve pH ˜8. Analysis of a small sample shows that some imine remains. The pH is further reduced to ˜3 with 2 N HCl. The reaction mixture is extracted with CH₂Cl₂. The organic phase is washed with water (3×500 mL) and brine (500 mL), then dried (Na₂SO₄) and concentrated under reduced pressure.

2-Octyl-1-undecanol

2-Octyl-1-undecanal (150 g, 0.534 mol) and 3 A ethanol (250 mL) are charged to a 3-L round-bottom flask fitted with a magnetic stir bar and nitrogen inlet. Sodium borohydride (30.0 g, 0.793 mol) is carefully added over 15 min., and the mixture stirs at room temperature for 60 h. The reaction mixture is filtered twice and partitioned between water and hexanes. The layers are separated. The hexane layer is washed with water (2×500 mL) and brine (500 mL). The hexane layer is dried (Na₂SO₄) and concentrated. The residual oil is then stripped and vacuum distilled using a short-path distillation apparatus. A forerun fraction is collected (bp: 30-125° C., full vacuum). Distillation continues to collect the desired alcohol (bp: 135-160° C., full vacuum), as confirmed by ¹H NMR analysis.

Sodium 2-octyl-1-undecyl Sulfate

2-Octyl-1-undecanol (79.0 g) is added to a 0.5-L flask equipped with mechanical stirrer, nitrogen inlet, and reflux condenser. 1,4-Dioxane (400 mL) is added, and the mixture is stirred. Sulfamic acid (27.8 g) and urea (0.35 g) are added. The mixture is slowly heated to reflux (105° C.) and refluxing continues for 6 h. The mixture is cooled. Urea and residual sulfamic acid are removed by filtration. The mixture is concentrated to remove 1,4-dioxane. Methanol is added to the 2-octyl-1-undecyl sulfate ammonium salt, and then 50% aq. NaOH solution is added to achieve a pH of about 10.3. The resulting mixture, which contains sodium 2-octyl-1-undecyl sulfate, is stripped and analyzed (93.0% actives by ¹H NMR).

Procedure for Testing Laundry Detergent Samples

The procedure described earlier for use with the mid-chain headgroup surfactants prepared in Section I above is used again for detergency testing the alkylene-bridged surfactants prepared in this Section III.

IV. Performance of Alkylene-Bridged Surfactants in Cold-Water Cleaning

Tables 4 and 6 provide formulation details. The control formulation includes both a sodium linear alkylbenzene sulfonate (Na LAS) and a sodium C₁₂-C₁₄alcohol ethoxylate (3 EO) sulfate (Na AES). In Formulations F and H through L, the test surfactant replaces Na AES. In Formulation G, the test surfactant replaces Na LAS. Formulation I, which utilizes a C₂₀test surfactant, is comparative.

Tables 5 and 7 summarize the detergency performance results for cold-water cleaning of cotton fabric treated with bacon grease, butter, cooked beef fat, and beef tallow greasy soils. All formulations are tested at 0.1% actives levels. Wash cycles are 30 min in front-loading high-efficiency washing machines. The target performance (which corresponds to a ΔSRI value of 0.0) is that of a control cold-water detergent used with a cold-water wash (60° F.) and cold-water rinse (60° F.).

As Table 5 shows, replacement of the Na LAS or Na AES in the control cold-water high-efficiency detergent with sodium 2-hexyl-1-decyl sulfate (C₁₆) or a mixture of 2-octyl-1-decyl sulfate and 2-hexyl-1-dodecyl sulfate (C₁₈mixture) gives a remarkable improvement in cleaning greasy soils such as bacon grease, beef tallow, or cooked beef fat compared with the control formulation. In contrast, when a similar C₂₀material (2-octyl-1-dodecyl sulfate) is used instead, poorer results are obtained compared with the control formulations.

TABLE 4

Cold-Water Liquid Laundry Detergent Formulations

Formulation (wt. %)

Control
F
G
H
I*

Sodium citrate dihydrate
3.5
3.5
3.5
3.5
3.5

Biosoft ® S-101 (97.4%) HLAS
8.1
8.1
—
8.1
8.1

NaOH (50%)
2.0
1.0
—
1.0
1.0

Monoethanolamine, 99%
2.1
2.1
2.1
2.1
2.1

Neodol ® 25-7
11.9
11.9
11.9
11.9
11.9

Stepanate ® SCS (44.9%) (Na
2.5
2.5
2.5
2.5
2.5

cumene sulfonate)

Coco fatty acid, Emry 622 (100%)
2.95
2.95
2.95
2.95
2.95

Sodium C₁₂-C₁₄alcohol
7.74
—
7.74
—
—

ethoxylate (3 EO) sulfate (100%)

Sodium 2-hexyl-1-decyl sulfate
—
8.0
8.1
—
—

(96.9%)

Sodium 2-octyl-1-decyl/2-hexyl-1-
—
—
—
7.9
—

dodecyl sulfate (98.5%)

Sodium 2-octyl-1-dodecyl sulfate
—
—
—
—
8.1

(96.1%)

Deionized water
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%

adjusted pH
8.8
8.5
8.6
8.5
8.5

*Comparative example

TABLE 5

Detergency Performance in Cold-Water Cleaning Greasy

Soil Stain Set

ΔSRI of Cleaning Data at

60° F. wash/60° F. rinse

Test formulation (0.1%
Bacon

Cooked Beef
Beef

actives)
Grease
Butter
Fat
Tallow

Na LAS/Na AES (3 EO)/
0.0
0.0
0.0
0.0

Neodol ® 25-7 (control)

Sodium 2-hexyl-1-decyl
4.50
0.27
3.92
9.63

sulfate/Na LAS/Neodol ®

25-7 (Formulation F)

Sodium 2-hexyl-1-decyl
3.35
0.57
2.58
8.65

sulfate/Na AES (3

EO)/Neodol ® 25-7

(Formulation G)

Sodium 2-octyl-1-decyl/2-
3.49
0.33
1.15
10.19

hexyl-1-dodecyl sulfate/

Na LAS/Neodol ® 25-7

(Formulation H)

Sodium 2-octyl-1-dodecyl
1.67
−0.29
0.69
−0.46

sulfate/Na LAS/Neodol ®

25-7 (Formulation I)*

*Comparative example

TABLE 6

Cold-Water Liquid Laundry Detergent Formulations

Formulation (wt. %)

Control
J
K
L

Sodium citrate dihydrate
3.5
3.5
3.5
3.5

Biosoft ® S-101 (97.4%) HLAS
8.1
8.1
8.1
8.1

NaOH (50%)
2.0
1.0
1.0
1.0

Monoethanolamine, 99%
2.1
2.1
2.1
2.1

Neodol ® 25-7
11.9
11.9
11.9
11.9

Stepanate ® SCS (44.9%) (Na
2.5
2.5
2.5
2.5

cumene sulfonate)

Coco fatty acid, Emry 622
2.95
2.95
2.95
2.95

(100%)

Sodium C₁₂-C₁₄alcohol
7.74
—
—
—

ethoxylate (3 EO) sulfate

(100%)

Sodium 2-hexyl-1-nonyl sulfate
—
8.7
—
—

(88.9%)

Sodium 2-heptyl-1-decyl
—
—
7.9
—

sulfate (98.5%)

Sodium 2-octyl-1-undecyl
—
—
—
8.1

sulfate (96.1%)

Deionized water
q.s. to 100%
q.s. to 100%
q.s. to 100%
q.s. to 100%

adjusted pH
8.8
8.5
8.5
8.5

TABLE 7

Detergency Performance in Cold-Water Cleaning Greasy Soil

Stain Set

ΔSRI of Cleaning Data at

60° F. wash/60° F. rinse

Test formulation (0.1%
Bacon

Cooked
Beef

actives)
Grease
Butter
Beef Fat
Tallow

Na LAS/Na AES (3 EO)/
0.0
0.0
0.0
0.0

Neodol ® 25-7 (control)

Sodium 2-hexyl-1-nonyl
3.66
0.33
3.81
10.50

sulfate/Na LAS/Neodol ® 25-7

(Formulation J)

Sodium 2-heptyl-1-decyl
2.88
−0.25
1.36
8.40

sulfate/Na LAS/Neodol ® 25-7

(Formulation K)

Sodium 2-octyl-1-undecyl
2.65
−0.28
2.92
4.19

sulfate/Na LAS/Neodol ® 25-7

(Formulation L)

As Table 7 shows, replacement of the sodium C₁₂-C₁₄alcohol ethoxylate (3 EO) sulfate (Na AES) in the control cold-water high-efficiency detergent with sodium 2-hexyl-1-nonyl sulfate (C₁₅), sodium 2-heptyl-1-decyl sulfate (C₁₇), or 2-octyl-1-undecyl sulfate (C₁₉) gives a substantial improvement in cleaning greasy soils such as bacon grease, beef tallow, or cooked beef fat compared with the control formulation.

Liquefaction Experiment and Microscopy Evaluation

A Keyence VH-Z100U microscope equipped with a universal zoom lens RZ (×100-×1000) and cold stage is used. Slides are prepared by applying a small dab of beef tallow soil to a glass slide. The soil sample is covered with a glass slide cover and pressed gently to form a thin film. The slide is placed on a cold stage platform of the microscope, which is set at 15° C., and is allowed to equilibrate for 10 minutes. Magnification is set at ×200 and focused to visualize the beef tallow soil/air boundary. Video recording is initiated. A drop of 0.1% active experimental or control surfactant previously equilibrated at 15° C. is carefully introduced between the cover slide and the glass slide containing the beef tallow soil. The surfactant solution is then allowed to diffuse via capillary action and come into contact with beef tallow soil. The process involving the interaction between the surfactant solution and beef tallow soil is recorded. Observations are made for formation (or lack of formation) of oily droplets at the beef solid (beef tallow)/liquid (surfactant solution) boundary. Results appear in Table 8.

TABLE 8

Liquefaction of Beef Tallow in Water at 15° C.

Liquefaction (formation of oily

droplets at the solid

(beef tallow)/liquid (surfactant

Test surfactant (0.1% active)
solution) interface observed

Sodium 2-hexyl-1-decyl sulfate
Yes (~5-10 minutes)

Sodium 2-heptyl-1-decyl sulfate
Yes (~5-10 minutes)

Sodium lauryl sulfate (Stepanol ®
No

WAC-Extra), control

Sodium lauryl ether (3 EO) sulfate
No

(Steol ® CS-330), control

As shown in Table 8, the alkylene-bridged surfactants rapidly liquefy beef tallow in dilute aqueous media at low temperature under static conditions, while the control surfactants are ineffective in doing so.

The preceding examples are meant only as illustrations; the following claims define the invention.

Number	Name	Date	Kind
5349101	Lutz	Sep 1994	A
6468213	Knell	Oct 2002	B1
7629305	Szekeres	Dec 2009	B1
20060247148	Ortiz	Nov 2006	A1

Number	Date	Country
19524287	Jan 1997	DE
H08188793	Jul 1996	JP
2013503964	Feb 2013	JP
2014064562	Apr 2014	JP

	Number	Date	Country
	62009581	Jun 2014	US
	62009595	Jun 2014	US

	Number	Date	Country
Parent	15353968	Nov 2016	US
Child	16536863		US

	Number	Date	Country
Parent	PCT/US2015/034652	Jun 2015	US
Child	15353968		US

Detergents for cold-water cleaning

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