WO2003037837A2 - Precurseurs de tensioactifs disubstitues et tensioactifs obtenus - Google Patents

Precurseurs de tensioactifs disubstitues et tensioactifs obtenus Download PDF

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WO2003037837A2
WO2003037837A2 PCT/US2002/033672 US0233672W WO03037837A2 WO 2003037837 A2 WO2003037837 A2 WO 2003037837A2 US 0233672 W US0233672 W US 0233672W WO 03037837 A2 WO03037837 A2 WO 03037837A2
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independently
substituted
carbon atoms
surfactant
compound
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PCT/US2002/033672
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WO2003037837A3 (fr
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Christopher J. Tucker
Thomas H. Kalantar
Promod Kumar
Gary M. Strandburg
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Dow Global Technologies Inc.
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Publication of WO2003037837A3 publication Critical patent/WO2003037837A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
    • C07C305/10—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • This invention is for di-substituted surfactant precursors and surfactants prepared from them, methods of making the di-substituted surfactant precursors and derived surfactants.
  • this invention relates to the production of di-substituted surfactant precursors.
  • ⁇ , ⁇ -diols and ⁇ , ⁇ -di-substituted compounds may be prepared by the ring opening of substituted three member heterocyclic rings such as pentane- 1,2-oxide.
  • pentane- 1,2-diol may be prepared by the acid catalyzed hydrolysis of 1,2-epoxy pentane [see, Sandier & Karo, Organic Functional Group Preparation, Vol. 1, pl04].
  • hydrophobic epoxides substantially insoluble in water, and whose hydrolysis products are substantially insoluble in water
  • hydrophobic diol compounds can only be completely hydrolyzed in aqueous systems containing an organic co-solvent.
  • hydrolysis of substantially water-insoluble epoxides in water is generally incomplete, or difficult to drive to completion (hydrolysis may, for example, require temperatures in excess of 100 degrees Celsius and/or very long reaction times to ensure completion of reaction), and, further, that ethers, rather than the desired diol, may be the substantive product.
  • this invention relates to surfactants prepared from the precursors.
  • Surfactants based on linear alcohols e.g., linear alcohol alkoxylates, alkyl sulfates and alkyl ether sulfates
  • these surfactants have acceptable surfactant properties and are readily biodegradable.
  • liquid dishwashing detergents, liquid laundry detergents, and powdered laundry detergents have all been offered to the consumer at significantly higher surfactant concentrations than traditionally.
  • a modern laundry detergent provides surfactant in about 3 ounces (88.72 ml) of detergent material, compared to an equivalent laundry detergent as provided in 1 cup (236.6 ml) of detergent material in the 1970s; the concentration of the surfactant in today's detergent is commensurately about 30% greater than was the case in the 1970s.
  • These higher concentrations along with changes in washing temperatures [the average wash temperature in the 1970s was about 105 degrees F (40.5 °C) as compared to an average modern wash temperature of about 95 degrees F (35 °C)] establish a set of criteria which must be acceptably resolved by the modern surfactant molecule of choice.
  • linear alcohol-based surfactants have a room- temperature viscosity well above 10,000 centipoise, where a maximum of about 300 centipoise in a liquid detergent is needed for utility in the normal laundry application.
  • solvents such as ethanol and propylene glycol
  • agglomerated powdered detergent processes there is a need today for highly active and pumpable surfactant pastes (greater than 80% surfactant by weight) to minimize energy costs associated with removing excess water.
  • linear alcohol ethoxylates having hydrophobic groups of about 12 carbon atoms or more have low critical micelle concentrations, a desirable property in surfactants.
  • linear alcohol ethoxylates also exhibit broad gel regions (viscosity greater than 10,000 cps) when mixed with water. Generally these gel regions begin at around 30 weight percent surfactant and continue at concentrations of greater than 80 weight percent of surfactant (see, Shell Chemical Company, Neodol ® Ethoxylate and competitive Nonionics Properties Guide, 1994). This property limits the amount of surfactant capable of being incorporated into the final product, unless large amounts of solvents (such as ethanol and propylene glycol) are used.
  • solvents such as ethanol and propylene glycol
  • Linear alcohol ethoxylates with hydrophobic groups of about 10 carbon atoms or less mitigate, to some extent, the broad gel regions, but have undesirable odors associated with them.
  • surfactants based on these shorter hydrophobes have relatively high critical micelle concentrations. Surfactants with high critical micelle concentrations have low effectiveness, thus limiting their use in many detergent applications. This is especially true in liquid laundry detergents and liquid hand dishwashing detergents where a small amount of product is diluted with copious amounts of water.
  • Secondary alcohol ethoxylates having hydrophobic groups of about 12 carbon atoms or more have properties that fall somewhere between. That is, these surfactants offer a compromise between these properties but do not address the deficiency adequately.
  • the present invention concerns a di-substituted surfactant precursor compound represented by the following formula
  • R" independently is G
  • n is an integer having a value between 0 and 20;
  • R a is, independently, R ! XZ, R*Z, R X, or R 1 where R a has between 4 and 30 carbon atoms;
  • R 1 is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group;
  • Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like;
  • G is, independently,
  • R 3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and
  • X is, independently,
  • R c is n-C 10 H 21 ; and any mixture thereof.
  • the present invention concerns a blend of at least one compound of formula R'R" n R"' (formula I) as described hereinbefore with a compound of formula II
  • the present invention concerns a blend of between 0.1 weight percent and 99.9 weight percent of a ⁇ , ⁇ -di-substituted compound having the following formula III
  • R is, independently, XZC, ZC, XC, or C, and X, Z, R , R , and G are as defined hereinbefore and,
  • At least one di-substituted surfactant precursor compound having the formula R'R" n R"' (formula I) wherein R', R", R'" and n are as defined hereinbefore.
  • the present invention concerns a method for preparing the above di- substituted surfactant precursor compounds of formula R'R" n R'" (formula I) wherein R', R", R"' and n are as defined hereinbefore which method comprises the steps of:
  • a substituted three-membered heterocycle compound having between 6 and 32 carbon atoms selected from the group consisting of a substituted 1- oxacyclopropane, a substituted 1-thiacyclopropane, and a substituted 1- azacyclopropane,
  • the amount of heterocycle compound is not critical to the practice of the process of this invention.
  • a suitable amount of the heterocycle compound to be used in this process would be readily known to a person of an ordinary skill in the art and would, in general, depend on the size of the reaction vessel used.
  • the amount of heterocycle compound would be from about 1 to about 70, preferably from about 2 to about 50, most preferably from about 2 to about 25, percent by weight.
  • the present invention concerns a surfactant made through treating the di-substituted surfactant precursor compound of formula R'R" n R" (formula I) obtained in the above described process by additional steps of:
  • the di-substituted surfactant precursor compound employed in the above mentioned process for the preparation of the surfactant product can be either di-substituted precursor compound of formula I hereinbefore, a blend of two or more di-substituted precursor compounds of formula I hereinbefore, a blend of at least one di-substituted precursor compound of formula I hereinbefore and ⁇ , ⁇ -di-substituted compound of formula III hereinbefore, or a blend of two or more ⁇ , ⁇ -di-substituted compound of formula III hereinbefore.
  • the present invention concerns a surfactant comprising a compound having the following formula
  • R' comprises R- or R a ⁇ R J
  • R" independently comprises- -R a
  • R"' comprises G R J
  • n is an integer having a value between 0 and 20;
  • J is, independently, any of SO 3 M, PO(OM) 2 , ZCO 2 M, H, an alkoxylene monomeric unit having between 2 to 4 carbon atoms or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms or any mixture thereof, an alkoxylene monomeric unit having between 2 to 4 carbon atoms wherein said alkoxylene is capped with a functional group selected from the group consisting of SO 3 M and PO(OM) 2 and ZCO 2 M and H or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms and wherein said polyalkoxylene is capped with a functional group selected from the group consisting of SO 3 M and PO(OM) and ZCO 2 M and H or any mixture thereof, wherein M is either a monovalent cation, for example, sodium, potassium, ammonium and C 1-24 alkylammonium
  • R a is, independently, R ! XZ, R ⁇ , R X, or R 1 with the proviso that R a has between 4 and 30 carbon atoms;
  • R 1 is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group;
  • Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like;
  • G is, independently,
  • R is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl isopropyl and the like; and
  • X is, independently,
  • R° is n-C 10 H 21 ; or a blend of two or more compounds of formula R'R" n R'" (formula IN) wherein R', R", R'" and n are as defined in above.
  • the present invention concerns a surfactant blend of at least one compound having formula IN as described hereinbefore with a compound of formula N
  • the present invention concerns a surfactant blend of between 0.1 weight percent and 99.9 weight percent of an ⁇ , ⁇ di-substituted compound having formula Nl
  • R" independently is G -R a
  • n is an integer having a value between 0 and 20;
  • J is, independently, any of SO 3 M, PO(OM) 2 , ZCO M, H, an alkoxylene monomeric unit having between 2 to 4 carbon atoms or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms or any mixture thereof, an alkoxylene monomeric unit having between 2 to 4 carbon atoms wherein said alkoxylene is capped with a functional group selected from the group consisting of SO 3 M and PO(OM) 2 and ZCO 2 M and H or any mixture thereof, a polyalkoxylene of between 2 and 100 monomeric repeating units wherein each monomeric unit has between 2 to 4 carbon atoms and wherein said polyalkoxylene is capped with a functional group selected from the group consisting of SO 3 M and PO(OM) 2 and ZCO M and H or any mixture thereof, wherein M is either a monovalent cation, for example, sodium, potassium, ammonium and C 1-24 alkylammonium c
  • R a is, independently, R XZ, R ! Z, R*X, or R 1 with the proviso that R a has between 4 and 30 carbon atoms;
  • R b is, independently, XZC, ZC, XC, or C;
  • R 1 is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group;
  • Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like;
  • G is, independently,
  • R 3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and
  • X is, independently, s O
  • the present invention concerns a surfactant having the following properties:
  • This invention uses a process of hydrolyzing a substituted three-membered heterocycle having between 6 and 32 carbon atoms (a substituted 1-oxacyclopropane, a substituted 1- thiacyclopropane, or a substituted 1-azacyclopropane; preferably a hydrophobic epoxide having a Hildebrand solubility parameter between about 16.307 and about 16.924 (joules/cm 3 ) 1/2 such as hexylene oxide, octylene oxide, and the like).
  • this invention is embodied as a process for hydrolyzing a hydrophobic epoxide in water to prepare a diol product that contains varying levels of diol and ethers.
  • the rate of the reaction and the ratio of diol to ether is efficaciously controlled by conducting the hydrolysis of the epoxide in water by adding a surfactant in an amount sufficient to disperse the epoxide in the water as an emulsion, and by adding a hydrolysis catalyst, such as, without limitation, H 2 SO 4 or HClO 4 , with stirring adequate to sustain this emulsion, and heating to temperatures less than or equal to 100 degrees Celsius. Without surfactant, the reaction is incomplete. With 5% Sodium Dodecyl Sulfate (SDS) and H 2 SO 4 as catalyst, the reaction yields 99% diol-ether product.
  • SDS Sodium Dodecyl Sulfate
  • H 2 SO 4 HClO 4
  • R a is, independently, R*XZ, R ! Z, R*X, or R 1 with the proviso that R a has between 4 and 30 carbon atoms;
  • R 1 is, independently, a substituted or unsubstituted hydrocarbon group having from 1 to 28, preferably from 4 to 20, most preferably from 6 to 16, carbon atoms such as an alkyl, substituted alkyl, aryl, or alkaryl group;
  • Z is, independently, a substituted or unsubstituted, linear or branched hydrocarbylene group having from 1 to 10 carbon atoms, such as methylene, ethylene, 1,3 propylene and the like;
  • G is, independently,
  • R 3 is, independently, H or a linear or branched hydrocarbyl group having from 1 to 20, preferably from 1 to 12, most preferably from 1 to 4, carbon atoms such as methyl, ethyl, propyl, isopropyl and the like; and
  • X is, independently,
  • Non-limiting examples of the hydrocarbon group contemplated by the substituent R in the above described formulae are n-octyl, 1,1,1-trimethylpentyl, n-decyl, n-dodecyl, n- tetradecyl, n-hexadecyl, n-dodecyl, and the like.
  • Non-limiting examples of the hydrocarbylene group contemplated by the substituent Z in the above described formulae are methylene, ethylene, 1,2-propylene, 1,3 -propylene, 1,4- butylene, and the like.
  • Non-limiting examples of the hydrocarbyl group contemplated by the substituent R 3 in the above described formulae are methyl, ethyl, n-propyl, n-butyl, iso-propyl, isobutyl, tertiary-butyl, and the like.
  • the diol mixtures formed above may be hydrophilized (i.e. further reacted to add a hydrophilic group) to form surface active agents that have been found to have surprising and useful properties.
  • the hydrophilicization step may include, without limitation, alkoxylation, sulfation, phosphation, or carboxylation.
  • Alkoxylation of a diol product is achieved by methods known in the art, for example, by adding a base catalyst to the diol product, removing substantially all water, and then reacting with an organic epoxide or any combination of organic epoxides.
  • organic epoxides useful in the present process are ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO).
  • Sulfation may be achieved by reaction with ClSO H or SO 3 reagents, as is well known in the art.
  • Phosphation may be achieved by reaction with P 2 O 5 or anhydrous H 3 PO 4 as is known in the art.
  • Carboxylation may be achieved by reacting the diol mixture in the presence of a base with chloroacetic acid, for example.
  • the polyalkoxylene-hydrophilicized diol product may be converted to an anionic product by further reaction of the diol mixture polyalkoxylene ether to form a sulfate, phosphate, or carboxylate.
  • surfactants are alternatively monomeric surfactants, mixtures of monomeric and polymeric surfactants, or polymeric surfactants.
  • surfactants that have low critical micelle concentrations yet do not experience broad gel regions when mixed with water. This novel property circumvents the limitations of surfactants known to the art.
  • surfactants include, without limitation, sulfates, alkoxylates, polyalkoxylates, phosphates, carboxylates, and sulfates, carboxylates and phosphates of alkoxylates or polyalkoxylates or mixtures thereof.
  • the following examples are provided to more fully illustrate the present invention but are not intended to be, nor should they be construed as being, limiting in any way of the scope of the invention.
  • Example 1 The process of Example 1 was repeated except that tetradecane-1, 2-oxide was added neat, without surfactant. After 4 hours, as sample was taken. SFC analysis of the diluted sample showed incomplete consumption of the starting material, and formation of some 1,2- tetradecanediol and ethers derived from that diol ( ⁇ 81: 13:0.75 mass ratio of tetradecane-1 -2- oxide to 1-2-tetradecanediol to ethers respectively by SFC analysis).
  • Example 2 Hydrolysis of hexene- 1,2-oxide: the process of Example 1 was repeated except hexene oxide was used as the substrate. After 4 hours, a sample was taken. GC analysis showed that the epoxide was largely consumed, and that the diol was formed ( ⁇ 90 diol: 5 hexene mass ratio by SFC analysis). SFC analysis showed trace levels of ethers ( «1%).
  • Example 2
  • Example 4 Ethoxylation of dodecane- 1,2-diol: Into a 2 gallon stirred reactor were loaded 2564 g dodecane- 1,2-diol and 2.85 g KOH. The mixture was heated and stirred under vacuum at 130 °C to remove the residual water to a level of 62 ppm. 1710 g ethylene oxide were then added over 4 hours, followed by reaction for 2 more hours at 130 °C. 1800 g dodecane- l,2-diol-3.3- ethoxylate were drained from the reactor. 870 g EO were added to the reactor as above. 1116 g dodecane- l,2-diol-6-ethoxylate were drained from the reactor.
  • the organic layer was washed with 4 x 100 mL 0.5 N NaOH, the 4 x 100 mL brine. The pH of the resulting final brine layer was 5-6. Solids that had separated out of the organic layer were filtered off and saved. The filtrate was dried over Na 2 SO 4 (anhydrous) and filtered. The initial filtrand was added back to the now dry ethyl acetate solution. The product was combined with the products of 2 smaller scale hydrolyses (each at 50 g dodecane- 1,2-oxide) and the solution rotovaped to dryness. The composition of the resulting solid dodecanediol product was (diol:ethers) 40:56 mass ratio by SFC analysis. The total mass recovered was 635 g (91% mass recovery).
  • aqueous gel region was found across the entire dilution range (22 °C) for the mixture, compared to a gel region starting at 60 wt% for the l,2-dodecanediol-6-ethoxylate, and a gel region starting at 35 wt% for Neodol 23-9 (whose CMC is 0.003 wt%).
  • Neither the 1,2- dodecanediol-9.4-ethoxylate or the mixture exhibited a gel point across the entire aqueous dilution range (22 °C), compared to a gel region starting at 35 wt% for Neodol 23-9 (whose CMC is 0.003).
  • Cloud Point Physical properties (aqueous viscosity, Critical Micelle Concentration, Cloud Point) for alkane diol ethoxylates and alkane diol/alkane diol oligomer ethoxylate blends have been determined experimentally. Cloud Points were determined using a Mettler Model FP800 Thermosystem fitted with a FP81 measuring cell. Cloud points were determined at concentrations of 1 weight percent surfactant and were done in triplicate with the standard deviation ⁇ 0.2°C.
  • Aqueous viscosities were measured using a Brookfield Model DV-III Rheometer fitted with a small sample adapter. All measurements were taken at 23 °C, at 3 rpm, using spindle number 18 unless noted. The viscosities listed are averages of four measurements.
  • the term gel denotes a non-flowing, transparent liquid. The gels were not characterized further.
  • CMCs Critical micelle concentrations
  • Transmittance was used to quantify the transparency of the surfactant admixtures to ensure the admixtures made at ten weight percent surfactant are transparent single phase micellar solutions. Transmittance is defined at the ratio of the intensity of the transmitted beam (P) to the intensity of the incident beam (P 0 ). The transmittance is reported as the % transmittance or (P/P 0 ) x 100. All measurements were taken at 22°C using a Brinkman Model PC 910 Colorimeter fitted with a probe tip having a path length of 2 cm. Measurements were done at a wavelength of 650 nm after calibrating the instrument against de-ionized water such that de-ionized water would have a transmittance of 100%. The surfactant admixtures made at ten weight percent of surfactant were judged to be transparent single phase micellar solutions if they had %transmittance values of greater than 75%.
  • Table 1 summarizes the aqueous solution properties of selected important nonionic surfactant families along with examples of the preferred compositions.
  • the nomenclature used for the surfactants of the current art is C-x-yEn where x and y denote the number of carbon atoms in the hydrophobic group and n denotes the average number of moles of ethylene oxide that has been condensed with each mole of hydrophobe.
  • the inventive surfactants are surfactants A, B and C.
  • Surfactant A is an admixture of (a) 95% by weight of 1,2-dodecane diol ethoxylated to an average of about 5.5 moles of ethylene oxide and (b) 5% by weight of a polymeric di- substituted ether ethoxylated to an average of about 2.7 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.
  • Surfactant B is an admixture of (a) 90% by weight of 1,2-dodecane diol ethoxylated to an average of about 6 moles of ethylene oxide and (b) 10% by weight of a polymeric di- substituted ether ethoxylated to an average of about 2.7 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.
  • Surfactant C is an admixture of (a) 60% by weight of 1,2-dodecane diol ethoxylated to an average of about 9 moles of ethylene oxide and (b) 40% by weight of a polymeric di- substituted ether ethoxylated to an average of about 4.4 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C.
  • CMC and cloud point is given for each surfactant.
  • the cloud point is an important variable as it is an indicator of the hydrophilic/lipophillic nature of the surfactant. Similar cloud points indicate similar hydrophilic/hydrophobic properties and ensure that the comparisons between surfactants are meaningful.
  • compositions give both low critical micelle concentrations and low aqueous solution viscosities across the entire dilution range.
  • the low viscosity property is also observed with sodium salts of sulfated 1,2-alkanediol ethoxylates.
  • Table 2 lists aqueous viscosity data for selected surfactants.
  • the surfactants are based on 1,2-alkane diols having an average of three moles of ethylene oxide of examples 8-11.
  • the terms MS and DS denote mono-sulfate and di-sulfate.
  • the commercial product is a sodium salt of a mono-sulfated lauryl alcohol ethoxylate having an average of two moles of ethylene oxide.
  • Formulations were prepared with surfactants of the instant invention as shown in Table 3 where (a) Surfactant 1 is a mixture of (1) about 60% by weight of 1,2-dodecane diol ethoxylated to an average of about 9 moles of ethylene oxide and (2) about 40% by weight of a polymeric di-substituted ether ethoxylated to an average of about 4.4 moles of ethylene oxide such that the admixture has a cloud point of about 75 °C and (b) Surfactant 2 is a mixture of (1) about 60% by weight of the di-sodium salt of 1,2-dodecanediol ethoxylated to an average of about three moles of ethylene oxide capped with about two sulfate groups and (2) about 40% by weight of the di-sodium salt of a polymeric di- substituted ether ethoxylated to an
  • compositions have a relatively low level of ethanol and propylene glycol. These solvents are generally added to reduce the product viscosity that arises from the deficiencies in surfactants used in commercial practice.
  • Composition A contains only commercial surfactants known to the art.
  • Compositions B and C are prepared by substituting surfactants of the invention for their commercial counter parts. Even when the detergent compositions are prepared with small amounts of the inventive surfactants, the formulation viscosity is significantly reduced, eliminating the need for additional solvents.
  • a critical micelle concentration of not greater than about 0.005 weight percent of said surfactant in water when admixed with water at about 25 degrees C; an aqueous solution viscosity of less than 2500 centipoise for all admixtures of said surfactant in water when admixed with water at about 25 degrees C; and
  • Improved solution properties also provide for high active, liquid laundry detergents and high active, stable, pumpable and transportable surfactant pastes used in powdered detergents (reference US Patent 6,294,513, International Patent Publication WO 99/19453, International Patent Publication WO 99/19455, and International Patent Publication WO 99/19454).
  • the improvements are believed to be the result of the small branches, (predominantly methyl, ethyl, and propyl branches) which presumably disrupt surfactant packing efficiencies.
  • the small branches while having an impact on surfactant solution properties, do not appear to have a major impact on biodegradation rates.
  • These improvements provide surfactants having higher hydrophobicity than provided by surfactants derived from linear alcohols.
  • the described diol-based surfactants will provide improved performance in many applications when compared to mid-chain-branched surfactants.
  • the described diol-based surfactants should provide a lower formulation viscosity, thereby enabling (a) reduction or elimination of added solvents and (b) reduction in nonionic surfactant concentration.
  • the described diol-based surfactants also provide distinct advantages over surfactants based on linear and mid-chain-branched alcohols when either shorter chain surfactants or surfactants having enhanced hydrophilic properties are desired. These advantages derive from the extremely low levels of free diol in the alkoxylated product as compared to higher levels of free alcohol in the linear (or mid-chain-branched) alcohol alkoxylates.
  • Linear alcohol ethoxylates having 3 moles of ethylene oxide and linear alcohol ethoxylates having 6 moles of ethylene oxide contain approximately 32% and 9% free alcohol, respectively.
  • diol ethoxylates having 3 moles of ethylene oxide and diol ethoxylates containing 6 moles of ethylene oxide contain approximately 8% and less than 1% free diol, respectively. This facilitates better transfer of the surfactant to the interface since it does not have to compete with the alcohol.
  • This lower level of free diol should also be an advantage with respect to enzyme stability in liquid formulations. It is known that enzymes are more stable in alcohol ethoxysulfates than in alcohol sulfates. It is also known that low mole ethylene oxide linear alcohol ethoxylates (used for the production of linear alcohol ethoxysulfates) contain high levels of free linear alcohol. Therefore, upon sulfation, the resulting surfactant mixture Will contain high levels of alcohol sulfate. Since the described diol-based surfactants contain much lower levels of free diol, surfactant mixtures resulting from the sulfation of the low- mole diol-based ethoxylates will contain much lower levels of diol sulfate. Therefore, it is expected that the ethoxysulfates based on the described diol-based surfactants should be more compatible with enzyme systems in liquid formulations.
  • the low odor of the diol itself when coupled with the low level of free diol found in the diol alkoxylates will also greatly reduce the odor of C8-C12 alkoxylates. This is especially important in household product applications where these odors are seen as negative product attributes. Due to the odor problem, detergent manufactures frequently utilize C12-C14 ethoxylates.
  • the diol-based alkoxylates will allow manufacturers to utilize shorter-chain-length alkoxylates, which are more efficient hydrotropes. When this is combined with the enhanced properties of the described diol-based surfactants, significantly less surfactant should be needed as compared to surfactants based on linear alcohol ethoxylates or mid-chain branched ethoxylates.
  • Low-streaking surfactants are also known in the art. Examples of these are Alkyl Polyglycosides (Ref. Alkyl Polyglycosides, Technology, Properties and Applications; K. Hill, W. von Rybinski, G. Stall; VCH Publishing, 1996) and DOWFAX 3B2. It is believed that non-streaking surfactants are surfactants that do not experience gel regions at relatively high surfactant concentrations (>50% by weight.). Thus, hard surface (or all purpose) cleaners and window cleaner formulations based on these surfactants have been commercialized. It is expected that surfactants based on diols will also be non-streaking surfactants and thus be applicable to hard surface cleaners.
  • anionic and cationic surfactants derived from diol precursors have up to two charges per surfactant molecule, offering significant advantages over mono-valent ionic surfactant molecules. It is well known that anionic surfactants are very efficient at removing particulate soils such as dirt and clay. The anionic surfactant establishes a negative charge at the fabric/soil/water interface (creating a repulsive force on the particle, which is also negatively charged).
  • Surfactants having two anionic groups per molecule should be more efficient at building up the electrical charge; accordingly, fewer surfactant molecules should be needed, reducing amounts of surfactant required in the detergent formulation.
  • the same argument applies with respect to cationic surfactants; thus, lower concentrations of cationic surfactants should also be enabled in fabric softener formulations.
  • anionic surfactants presently used in laundry detergents have very high critical micelle concentrations (CMC), necessitating use of auxiliary (nonionic or cationic) surfactants in lowering the CMC of the detergent formulation.
  • CMC critical micelle concentration
  • auxiliary surfactants in lowering the CMC of the detergent formulation.
  • One advantage of the described diol-based anionic surfactants is that a surfactant can now be tailored to have both a low CMC and a low Kraft temperature (the temperature where the solubility of the anionic surfactant is equal to the CMC), reducing (or even eliminating) the need, for auxiliary surfactants in lowering the CMC of the detergent formulation.
  • One major disadvantage of monovalent anionic surfactants is their sensitivity to divalent metal ions.
  • a monovalent anionic surfactant When the cation of a monovalent anionic surfactant is exchanged with a divalent metal cation, a much more hydrophobic surfactant is formed (the divalent cation has two hydrophobic groups attached). That is not the case for the described divalent anionic diol-based surfactants.
  • tolerance for hardness ions should be significantly improved over anionic surfactants based on linear alcohols or mid-chain branched alcohols. This feature allows a much more hydrophobic anionic surfactant to be used without fear of surfactant precipitation in the presence of hardness ions.
  • Lower levels of detergent builder should be required with these types of surfactants.
  • increased levels of calcium can be added to liquid laundry detergent formulations without detrimental effects.
  • Surfactants are also a key component in emulsion polymerization. There has been significant work on the use of diol-based surfactants in emulsion polymerization (US Patent 4,549,002; US Patent 5,346,973; and Japanese Patent 59145028). The properties of the diol surfactants provide for greatly improved handling properties as well as for improved properties in an emulsion polymer. The described diol-based surfactants should also provide similar benefits in emulsion polymer formulations.
  • diol-based surfactants will be very suitable for many applications. These include but are not limited to: liquid laundry detergents, powered laundry detergents, laundry detergent tablets, laundry detergent pouches, hard surface cleaners, laundry pretreaters, bathroom cleaners, paints, emulsion polymers, coatings, agricultural applications, fabric softeners, carpet cleaners, liquid soaps, shampoos, and other applications that utilize nonionic, anionic, cationic, and amphoteric surfactants.
  • liquid laundry detergents An example to selectively illustrate, without limitation, specific teachings above is related to liquid laundry detergents. As previously noted, these products are now offered at higher surfactant concentrations than in the past.
  • One important surfactant found in liquid laundry detergents is based upon ethoxylated linear alcohols having hydrophobic groups of about 12 to 14 carbon atoms or more. These surfactants have low critical micelle concentrations, a desirable property in surfactants.
  • linear alcohol ethoxylates also exhibit broad gel regions (viscosity > 10,000 cps) when mixed with water.
  • these gel regions begin at around 30 weight percent surfactant and continue at concentrations of greater than 80 weight percent of surfactant (Shell Chemical Company, Neodol® Ethoxylate and competitive Nonionics Properties Guide, 1994). This property limits the amount of surfactant incorporated into the final product, unless large amounts of solvents (such as ethanol and propylene glycol) are used. Linear alcohol ethoxylates with hydrophobic groups of about 10 carbon atoms or less mitigate, to some extent, the broad gel regions, but have relatively high critical micelle concentrations.
  • surfactants of the current invention can be used to significantly modify the aqueous solution properties of surfactants known to the art as shown in the following Example 19.
  • the viscosity of a commercially available alcohol ethoxysulfate was measured (Steol® CS-230, Stepan Company, Northfield, IL).
  • the commercial product is an aqueous solution containing about 30% by weight of surfactant.
  • This product is compared to a mixture of lOg Steol CS-230, 3g TDD-3 MS, and 7g of Dl water. The resulting mixture is about 30% by weight of surfactant.
  • Aqueous viscosities were measured at 23 °C using a Brookfield Model DV-III Rheometer fitted with a small sample adapter.
  • the viscosity of Steol CS-230 was measured at 3 rpm, using spindle number 18.
  • the viscosity of the DDD-3 MS was measured at 6 rpm using spindle number 18.
  • the viscosity of Steol 230 (30% aqueous solution of a linear alcohol ethoxysulfate) is 25,000c ⁇ s.
  • the viscosity of a 1 : 1 mixture, by weight of Steol 230 and TDD-3MS, a diol ethoxysulfate, (30% aqueous solution) is 90cps, where TDD-3 MS is the mono-sulfate of tetradecane diol having an average of three moles of ethylene oxide.
  • TDD-3 MS and the Steol 230 have previously been referenced herein.

Abstract

L'invention a trait à des précurseurs de tensioactifs disubstitués, à des tensioactifs préparés à partir de ceux-ci, à des procédés de fabrication des précurseurs de tensioactifs disubstitués et des tensioactifs correspondants, et à des tensioactifs possédant les propriétés des tensioactifs décrits. On obtient les précurseurs de tensioactifs disubstitués et les tensioactifs en mélangeant de l'eau, un tensioactif, un catalyseur d'hydrolyse et une quantité initiale d'un hétérocycle à trois éléments substitué (un 1-oxacyclopropane substitué, un 1-thiacyclopropane substitué ou un 1-azacyclopropane substitué), et en maintenant le mélange en émulsion constitué du précurseur de tensioactif disubstitué, de l'eau, de l'hétérocycle, du tensioactif et du catalyseur pour former le précurseur de tensioactif disubstitué. Le précurseur de tensioactif disubstitué est en outre fonctionnalisé afin de présenter des propriétés hydrophiles voulues. L'invention permet d'obtenir un nouveau produit tensioactif possédant une nouvelle combinaison de propriétés (en mélange aqueux) de concentration critique de micelles, de viscosité et de transparence.
PCT/US2002/033672 2001-10-26 2002-10-22 Precurseurs de tensioactifs disubstitues et tensioactifs obtenus WO2003037837A2 (fr)

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