Classifications

• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2093—Esters; Carbonates
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/645—Mixtures of compounds all of which are cationic
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2044—Dihydric alcohols linear
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2048—Dihydric alcohols branched

Definitions

• the present invention relates to preferably translucent, or, more preferably, clear, aqueous, concentrated, liquid softening compositions useful for softening cloth. It especially relates to textile softening compositions for use in the rinse cycle of a textile laundering operation to provide excellent fabric-softening/static-control benefits, the compositions being characterized by, e.g., reduced staining of fabric, excellent water dispersibility, rewettability, and/or storage and viscosity stability at sub-normal temperatures, i.e., temperatures below normal room temperature, e.g., 25oC.
• Fabric softening compositions containing high solvent levels are known in the art. However, softener agglomerates can form and can deposit on clothes which can result in staining and reduced softening performance. Also, compositions may thicken and/or precipitate at lower temperatures, i.e., at about 40°F (about 4°C) to about 65°F (about 18°C). These compositions can also be costly for the consumer due to the high solvent levels associated with making a concentrated, clear product.
• the present invention provides concentrated aqueous liquid textile treatment compositions with low organic solvent level (i.e., below about 40%, by weight of the composition), that have improved stability (i.e., remain clear or translucent and do not precipitate, gel, thicken, or solidify) at normal, i.e., room temperatures and sub-normal temperatures under prolonged storage conditions.
• Said compositions also provide reduced staining of fabrics, good cold water dispersibility, together with excellent softening, anti-static and fabric rewettability characteristics, as well as reduced dispenser residue buildup and excellent freeze-thaw recovery.
• the object of the present invention is to provide aqueous, concentrated, translucent, or, preferably, clear, rinse-added liquid fabric softening compositions which provide one, or more benefits such as reduced staining on fabrics, ready dispersibility in rinse water, phase stability at low temperatures, and/or, preferably acceptable viscosity and viscosity stability at low temperatures, and/or recovery from freezing.
• compositions herein comprise:
• the present invention contains as an essential component from about 2% to about 80%, preferably from about 13% to about 75%, more preferably from about 17% to about 70%, and even more preferably from about 19% to about 65% by weight of the composition, of a fabric softener active selected from the compounds identified hereinafter, and mixtures thereof.
• the first type of DEQA preferably comprises, as the principal active, compounds of the formula
• each R substituent is H or a short chain C 1 -C 6 , preferably C 1 -C 3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is -O-(O)C-, -(R)N-(O)C-, -C(O)-N(R)-, or -C(O)-O-, preferably -O(O)C-, but not -OC(O)O-; the sum of carbons in each R 1 , plus one when Y is -O-(O)C- or -(R)N-(O)C-, is C 6 -C 22 , preferably C 14 -C 20 , but no more than one YR 1 sum being less than about 12 and then the other
• the Iodine Value of a "parent" fatty acid, or "corresponding" fatty acid is used to define a level of unsaturation for an R 1 group that is the same as the level of unsaturation that would be present in a fatty acid containing the same R 1 group.
• the counterion, X (-) above can be any softener-compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and the like, more preferably chloride.
• the anion can also, but less preferably, carry a double charge in which case X (-) represents half a group.
• Preferred biodegradable quaternary ammonium fabric softening compounds can contain the group -(O)CR 1 which is derived from unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.
• Non-limiting examples of DEQAs prepared from preferred fatty acids have the following approximate distributions: Fatty Acyl Group DEQA 1 DEQA 2 DEQA 3 DEQA 4 DEQA 5 C12 trace trace 0 0 0 C14 3 3 0 0 0 C16 4 4 5 5 5 C18 0 0 5 6 6 C14:1 3 3 0 0 0 C16:1 11 7 0 0 3 C18:1 74 73 71 68 67 C18:2 4 8 8 11 11 C18:3 0 1 1 2 C20:1 0 0 2 2 2 2 C20 and up 0 0 2 0 0 Unknowns 0 0 6 6 7 Total 99 99 100 100 102 IV 86-90 88-95 99 100 95 cis/trans (C18:1) 20-30 20-30 4 5 5 5 TPU 4 9 10 13 13 13
• Nonlimiting examples of DEQA's that can be blended, to form DEQA's of this invention are as follows: Fatty Acyl Group DEQA 10 DEQA 11 C14 0 1 C16 11 25 C18 4 20 C14:1 0 0 C16:1 1 0 C18:1 27 45 C18:2 50 6 C18:3 7 0 Unknowns 0 3 Total 100 100 IV 125-138 56 cis/trans (C18:1) Not Available 7 TPU 57 6
• DEQA 10 is prepared from a soy bean fatty acid
• DEQA 11 is prepared from a slightly hydrogenated tallow fatty acid.
• R 1 groups can comprise branched chains, e.g., from isostearic acid, for at least part of the R 1 groups.
• the total of active represented by the branched chain groups, when they are present, is typically from about 1% to about 90%, preferably from about 10% to about 70%, more preferably from about 20% to about 50%.
• Fatty Acyl Group DEQA 12 DEQA 13 DEQA 14 Isomyristic acid -- 1-2 -- Myristic acid 7-11 0.5-1 -- Isopalmitic acid 6-7 6-7 1-3 Palmitic acid 4-5 6-7 -- Isostearic acid 70-76 80-82 60-66 Stearic acid -- 2-3 8-10 Isoleic acid -- -- 13-17 Oleic acid -- -- 6-12 IV 3 2 7-12
• DEQA 12 - DEQA 14 are prepared from different commercially available isostearic acids.
• the more preferred DEQA's are those that are prepared as a single DEQA from blends of all the different fatty acids that are represented (total fatty acid blend), rather than from blends of mixtures of separate finished DEQA's that are prepared from different portions of the total fatty acid blend.
• the fatty acyl groups are unsaturated, e.g., from about 50% to 100%, preferably from about 55% to about 95%, more preferably from about 60% to about 90%, and that the total level of active containing polyunsaturated fatty acyl groups (TPU) be from about 3% to about 30%, preferably from about 5% to about 25%, more preferably from about 10% to about 18%.
• the cis/trans ratio for the unsaturated fatty acyl groups is usually important, with the cis/trans ratio being from 1:1 to about 50:1, the minimum being 1:1, preferably at least 3:1, and more preferably from about 4:1 to about 20:1. (As used herein, the "percent of softener active" containing a given R 1 group is the same as the percentage of that same R 1 group is to the total R 1 groups used to form all of the softener actives.)
• the highly unsaturated materials are also easier to formulate into concentrated premixes that maintain their low viscosity and are therefore easier to process, e.g., pump, mixing, etc.
• These highly unsaturated materials with only the low amount of solvent that normally is associated with such materials, i.e., from about 5% to about 20%, preferably from about 8% to about 25%, more preferably from about 10% to about 20%, weight of the total softener/solvent mixture, are also easier to formulate into concentrated, stable compositions of the present invention, even at ambient temperatures. This ability to process the actives at low temperatures is especially important for the polyunsaturated groups, since it mimimizes degradation. Additional protection against degradation can be provided when the compounds and softener compositions contain effective antioxidants, chelants, and/or reducing agents, as disclosed hereinafter.
• the present invention can contain medium-chain biodegradable quaternary ammonium fabric softening compound, DEQA, as a preferred component, having the above formula (1) and/or formula (2), below, wherein:
• the saturated C 8 -C 14 fatty acyl groups can be pure derivatives or can be mixed chainlengths.
• Suitable fatty acid sources for said fatty acyl groups are coco, lauric, caprylic, and capric acids.
• the groups are preferably saturated, e.g., the IV is preferably less than about 10, preferably less than about 5.
• substituents R and R 1 can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R 1 groups maintain their basically hydrophobic character.
• the preferred compounds can be considered to be biodegradable diester variations of ditallow dimethyl ammonium chloride (hereinafter referred to as "DTDMAC”), which is a widely used fabric softener.
• DTDMAC ditallow dimethyl ammonium chloride
• a preferred long chain DEQA is the DEQA prepared from sources containing high levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N-dimethyl ammonium chloride, where the acyl is derived from fatty acids containing sufficient polyunsaturation, e.g., mixtures of tallow fatty acids and soybean fatty acids.
• Another preferred long chain DEQA is the dioleyl (nominally) DEQA, i.e., DEQA in which N,N-di(oleoyl-oxyethyl)-N,N-dimethyl ammonium chloride is the major ingredient.
• Preferred sources of fatty acids for such DEQAs are vegetable oils, and/or partially hydrogenated vegetable oils, with high contents of unsaturated, e.g., oleoyl groups.
• Preferred medium chain DEQAs are dicocoyl DEQA (derived from coconut fatty acids), i.e., N,N-di(coco-oyl-oxyethyl)-N,N-dimethyl ammonium chloride, exemplified hereinafter as DEQA 6 , and N,N-di(lauroyl-oxyethyl)-N,N-dimethyl ammonium chloride.
• the diester when specified, it can include the monoester that is present.
• the DEQA can be DEQA monoester, e.g., one YR 1 group is either OH, or -C(O)OH, and, for Formula 1., m is 2.
• the corresponding diamide and/or mixed ester-amide can also include the active with one long chain hydrophobic group, e.g., one YR 1 group is either -N(R)H , or -C(O)OH.
• any disclosure, e.g., levels, for the monoester actives is also applicable to the monoamide actives.
• the percentage of monoester should be as low as possible, preferably no more than about 5%. However, under high, anionic detergent surfactant or detergent builder carry-over conditions, some monoester can be preferred.
• the overall ratios of diester to monoester are from about 100:1 to about 2:1, preferably from about 50:1 to about 5:1, more preferably from about 13:1 to about 8:1. Under high detergent carry-over conditions, the di/monoester ratio is preferably about 11:1.
• the level of monoester present can be controlled in manufacturing the DEQA.
• the above compounds, used as the biodegradable quaternized ester-amine softening material in the practice of this invention, can be prepared using standard reaction chemistry.
• an amine of the formula RN(CH 2 CH 2 OH) 2 where R is e.g., alkyl is esterified at both hydroxyl groups with an acid chloride of the formula R 1 C(O)Cl, to form an amine which can be made cationic by acidification (one R is H) to be one type of softener, or then quaternized with an alkyl halide, RX, to yield the desired reaction product (wherein R and R 1 are as defined hereinbefore).
• RX alkyl halide
• DEQA softener active that is suitable for the formulation of the concentrated, clear liquid fabric softener compositions of the present invention has the above formula (1) wherein one R group is a C 1-4 hydroxy alkyl group, preferably one wherein one R group is a hydroxyethyl group.
• An example of such a hydroxyethyl ester active is di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate, wherein the acyl group is the same as that of DEQA 1 , exemplified hereinafter as DEQA 8 .
• each Y, R, R 1 , and x (-) have the same meanings as before.
• Such compounds include those having the formula: [CH 3 ] 3 N (+) [CH 2 CH(CH 2 O(O)CR 1 )O(O)CR 1 ] Cl (-) where each R is a methyl or ethyl group and preferably each R 1 is in the range of C 15 to C 19 . Degrees of branching and substitution can be present in the alkyl or alkenyl chains.
• the anion X (-) in the molecule is the same as in DEQA (1) above.
• the diester when the diester is specified, it can include the monoester that is present.
• the amount of monoester that can be present is the same as in DEQA (1).
• DEQA 9 An example of a preferred DEQA of formula (2) is the "propyl" ester quaternary ammonium fabric softener active having the formula 1,2-di(acyloxy)-3-trimethylammoniopropane chloride, wherein the acyl group is the same as that of DEQA 5 , exemplified hereinafter as DEQA 9 .
• each R 1 is a hydrocarbyl, or substituted hydrocarbyl, group, preferably, alkyl, monounsaturated alkenyl, and polyunsaturated alkenyl groups, with the softener active containing polyunsaturated alkenyl groups being at least about 3%, preferably at least about 5%, more preferably at least about 10%, and even more preferably at least about 15%, by weight of the total softener active present; the actives preferably containing mixtures of R 1 groups, especially within the individual molecules, and also, optionally, but preferably, the saturated R 1 groups comprising branched chains, e.g., from isostearic acid, for at least part of the saturated R 1 groups, the total of active represented by the branched chain groups preferably being from about 1% to about 90%, preferably from about 10% to about 70%, more preferably from about 20% to about 50%.
• the DEQAs herein can contain a low level of fatty acid, which can be from unreacted starting material used to form the DEQA and/or as a by-product of any partial degradation (hydrolysis) of the softener active in the finished composition. It is preferred that the level of free fatty acid be low, preferably below about 10%, and more preferably below about 5%, by weight of the softener active.
• compositions of the present invention comprise less than about 40%, preferably from about 10% to about 35%, more preferably from about 12% to about 25%, and even more preferably from about 14% to about 20%, of the principal solvent, by weight of the composition.
• Said principal solvent is selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
• isopropyl alcohol is not very effective and has a strong odor.
• n-Propyl alcohol is more effective, but also has a distinct odor.
• Several butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a principal solvent system to minimize their odor.
• the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40oF (about 4.4oC) and are able to recover after storage down to about 20oF (about 6.7oC). It is also desirable for the ratio of the principal solvent to fabric softening active to be more than about 3, preferably from about 3 to about 100, more preferably from about 3.6 to about 50, and even more preferably from about 4 to about 25.
• any principal solvent for the formulation of the liquid, concentrated, preferably clear, fabric softener compositions herein with the requisite stability is surprisingly selective.
• Suitable solvents can be selected based upon their octanol/water partition coefficient (P).
• Octanol/water partition coefficient of a principal solvent is the ratio between its equilibrium concentration in octanol and in water.
• the partition coefficients of the principal solvent ingredients of this invention are conveniently given in the form of their logarithm to the base 10, logP.
• the logP of many ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
• the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p.
• the fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
• the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of the principal solvent ingredients which are useful in the present invention.
• Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
• the principal solvents herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said principal solvent preferably being asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes.
• asymmetric solvents appear to be very desirable, whereas the highly symmetrical solvents, having a center of symmetry, such as 1,7-heptanediol, or 1,4-bis(hydroxymethyl)cyclohexane, appear to be unable to provide the essentially clear compositions when used alone, even though their ClogP values fall in the preferred range.
• One can select the most suitable principal solvent by determining whether a composition containing about 27% di(oleyoyloxyethyl)dimethylammonium chloride, about 16-20% of principal solvent, and about 4-6% ethanol remains clear during storage at about 40°F (about 4.4°C) and recovers from being frozen at about 0°F (about -18°C).
• the most preferred principal solvents can be identified by the appearance of the freeze-dried dilute treatment compositions used to treat fabrics. These dilute compositions appear to have dispersions of fabric softener that exhibit a more unilamellar appearance than conventional fabric softener compositions. The closer to unilamellar the appearance, the better the compositions seem to perform. These compositions provide surprisingly good fabric softening as compared to similar compositions prepared in the conventional way with the same fabric softener active. The compositions also inherently provide improved perfume deposition as compared to conventional fabric softening compositions, especially when the perfume is added to the compositions at, or near, room temperature.
• Operable principal solvents are listed below under various listings, e.g., aliphatic and/or alicyclic diols with a given number of carbon atoms; monols; derivatives of glycerine; alkoxylates of diols; and mixtures of all of the above.
• the preferred principal solvents are in italics and the most preferred principal solvents are in bold type.
• the reference numbers are the Chemical Abstracts Service Registry numbers (CAS No.) for those compounds that have such a number. Novel compounds have a method identified, described hereinafter, that can be used to prepare the compounds.
• Some inoperable principal solvents are also listed below for comparison purposes.
• the inoperable principal solvents can be used in mixtures with operable principal solvents.
• Operable principal solvents can be used to make concentrated fabric softener compositions that meet the stability/clarity requirements set forth herein.
• diol principal solvents that have the same chemical formula can exist as many stereoisomers and/or optical isomers.
• Each isomer is normally assigned with a different CAS No.
• different isomers of 4-methyl-2,3-hexanediol are assigned to at least the following CAS Nos: 146452-51-9; 146452-50-8; 146452-49-5; 146452-48-4; 123807-34-1; 123807-33-0; 123807-32-9; and 123807-31-8.
• Cylic Diols and Derivatives 1-isopropyl-1,2-cyclobutanediol 59895-32-8 3-ethyl-4-methyl-1,2-cyclobutanediol 3-propyl-1,2-cyclobutanediol 3-isopropyl-1,2-cyclobutanediol 42113-90-6 1-ethyl-1,2-cyclopentanediol 67396-17-2 1,2-dimethyl-1,2-cyclopentanediol 33046-20-7 1,4-dimethyl-1,2-cyclopentanediol 89794-56-9 3,3-dimethyl-1,2-cyclopentanediol 89794-57-0 3,4-dimethyl-1,2-cyclopentanediol 70051-69-3 3,5-dimethyl-1,2-cyclopentanediol 89794-58-1 3-ethyl-1,2-cyclopentanediol 4,4
• 1,2-Cyclobutanediol 1-ethenyl-2-ethyl- 58016-14-1 3-Cyclobutene-1,2-diol, 1,2,3,4-tetramethyl- 90112-64-4 3-Cyclobutene-1,2-diol, 3,4-diethyl- 142543-60-0 3-Cyclobutene-1,2-diol, 3-(1,1-dimethylethyl)- 142543-56-4 3-Cyclobutene-1,2-diol, 3-butyl- 142543-55-3 1,2-Cyclopentanediol, 1,2-dimethyl-4-methylene- 103150-02-3 1,2-Cyclopentanediol, 1-ethyl-3-methylene- 90314-52-6 1,2-Cyclopentanediol, 4-(1 -propenyl) 128173-45-5 3-Cyclopentene-1,2-diol, 1-e
• EO means polyethoxylates, i.e., -(CH 2 CH 2 O) n H
• Me-En means methyl-capped polyethoxylates -(CH 2 CH 2 O) n CH 3
• 2(Me-En) means 2 Me-En groups needed
• PO means polypropoxylates, -(CH(CH 3 )CH 2 O) n H
• BO means polybutyleneoxy groups, (CH(CH 2 CH 3 )CH 2 O)nH
• n-BO means poly(n-butyleneoxy) or poly(tetramethylene)oxy groups -(CH 2 CH 2 CH 2 CH 2 O) n H.
• Aromatic Diols 1-phenyl-1,2-ethanediol 93-56-1 1-phenyl-1,2-propanediol 1855-09-0 2-phenyl-1,2-propanediol 87760-50-7 3-phenyl-1,2-propanediol 17131-14-5 1 -(3-methylphenyl)-1,3-propanediol 51699-43-5 1-(4-methylphenyl)-1,3-propanediol 159266-06-5 2-methyl-1 -phenyl-1,3-propanediol 139068-60-3 1 -phenyl-1,3-butanediol 118100-60-0 3-phenyl-1,3-butanediol 68330-54-1 1 -phenyl-1,4-butanediol 136173-88-1 2-phenyl-1,4-butanediol 95840-73-6 1 -phenyl-2,3
• C 1-2 mono-ols that provide the clear concentrated fabric softener compositions of this invention.
• Only one C 3 mono-ol, n-propanol provides acceptable performance (forms a clear product and either keeps it clear to a temperature of about 4°C, or allows it to recover upon rewarming to room temperature), although its boiling point (BP) is undesirably low.
• BP boiling point
• Of the C 4 mono-ols only 2-butanol and 2-methyl-2-propanol provide very good performance, but 2-methyl-2-propanol has a BP that is undesirably low.
• principal solvents which have two hydroxyl groups in their chemical formulas are suitable for use in the formulation of the liquid concentrated, clear fabric softener compositions of this invention. It is discovered that the suitability of each principal solvent is surprisingly very selective, dependent on the number of carbon atoms, the isomeric configuration of the molecules having the same number of carbon atoms, the degree of unsaturation, etc. Principal solvents with similar solubility characteristics to the principal solvents above and possessing at least some asymmetry will provide the same benefit. It is discovered that the suitable principal solvents have a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60.
• the 1,2-hexanediol is a good principal solvent, while many other isomers such as 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,4-hexanediol, and 2,5-hexanediol, having ClogP values outside the effective 0.15 - 0.64 range, are not.
• Examples and Comparative Examples I-A and I-B vide infra).
• C7 diol isomers there are more possible C7 diol isomers, but only the listed ones provide clear products and the preferred ones are: 1,3-butanediol, 2-butyl-; 1,4-butanediol, 2-propyl-; 1,5-pentanediol, 2-ethyl-; 2,3-pentanediol, 2,3-dimethyl-; 2,3-pentanediol, 2,4-dimethyl-; 2,3-pentanediol, 4,4-dimethyl-; 3,4-pentanediol, 2,3-dimethyl-; 1,6-hexanediol, 2-methyl-; 1,6-hexanediol, 3-methyl-; 1,3-heptanediol; 1,4-heptanediol; 1,5-heptanediol; 1,6-heptanediol; of which the most preferred are: 2,
• C 8 diol isomers there are even more C 8 diol isomers, but only the listed ones provide clear products and the preferred ones are: 1,3-propanediol, 2-(1,1-dimethylpropyl)-; 1,3-propanediol, 2-(1,2-dimethylpropyl)-; 1,3-propanediol, 2-(1-ethylpropyl)-; 1,3-propanediol, 2-(2,2-dimethylpropyl)-; 1,3-propanediol, 2-ethyl-2-isopropyl-; 1,3-propanediol, 2-methyl-2-(1-methylpropyl)-; 1,3-propanediol, 2-methyl-2-(2-methylpropyl)-; 1,3-propanediol, 2-tertiary-butyl-2-methyl-; 1,3-butanediol, 2,2-diethyl; 1,3-but
• Preferred mixtures of eight-carbon-atom-1,3 diols can be formed by the condensation of mixtures of butyraldehyde, isobutyraldehyde and/or methyl ethyl ketone (2-butanone), so long as there are at least two of these reactants in the reaction mixture, in the presence of highly alkaline catalyst followed by conversion by hydrogenation to form a mixture of eight-carbon-1,3-diols, i.e., a mixture of 8-carbon-1,3-diois primarily consisting of: 2,2,4-trimethyl-1,3-pentanediol; 2-ethyl-1,3-hexanediol; 2,2-dimethyl-1,3-hexanediol; 2-ethyl-4-methyl-1,3-pentanediol; 2-ethyl-3-methyl-1,3-pentanediol; 3,5-octanediol; 2,2-di
• EO means polyethoxylates
• En means -(CH 2 CH 2 O) n H
• Me-En means methyl-capped polyethoxylates -(CH 2 CH 2 O) n CH 3
• 2(Me-En) means 2 Me-En groups needed
• PO means polypropoxylates, -(CH(CH 3 )CH 2 O) n H
• BO means polybutyleneoxy groups, (CH(CH 2 CH 3 )CH 2 O) n H
• n-BO means poly(n-butyleneoxy) groups -(CH 2 CH 2 CH 2 CH 2 O) n H.
• some specific diol ethers are also found to be suitable principal solvents for the formulation of liquid concentrated, clear fabric softener compositions of the present invention. Similar to the aliphatic diol principal solvents, it is discovered that the suitability of each principal solvent is very selective, depending, e.g., on the number of carbon atoms in the specific diol ether molecules.
• di(hydroxyalkyl) ethers The same narrow selectivity is also found for the di(hydroxyalkyl) ethers. It is discovered that bis(2-hydroxybutyl) ether, but not bis(2-hydroxypentyl) ether, is suitable. For the di(cyclic hydroxyalkyl) analogs, the bis(2-hydroxycyclopentyl) ether is suitable, but not the bis(2-hydroxycyclohexyl) ether. Non-limiting examples of synthesis methods for the preparation of some preferred di(hydroxyalkyl) ethers are given hereinafter.
• the butyl monoglycerol ether (also named 3-butyloxy-1,2-propanediol) is not well suited to form liquid concentrated, clear fabric softeners of the present invention.
• its polyethoxyiated derivatives preferably from about triethoxylated to about nonaethoxylated, more preferably from pentaethoxylated to octaethoxylated, are suitable principal solvents, as given in Table VI.
• Preferred aromatic glyceryl ethers include: 1,2-propanediol, 3-phenyloxy-; 1,2-propanediol, 3-benzyloxy-; 1,2-propanediol, 3-(2-phenylethyloxy)-; 1,2-propanediol, 1,3-propanediol, 2-(m-cresyloxy)-; 1,3-propanediol, 2-(p-cresyloxy)-; 1,3-propanediol, 2-benzyloxy-; 1,3-propanediol, 2-(2-phenylethyloxy)-; and mixtures thereof.
• the more preferred aromatic glyceryl ethers include: 1,2-propanediol, 3-phenyloxy-; 1,2-propanediol, 3-benzyloxy-; 1,2-propanediol, 3-(2-phenylethyloxy)-; 1,2-propanediol, 1,3-propanediol, 2-(m-cresyloxy)-; 1,3-propanediol, 2-(p-cresyloxy)-; 1,3-propanediol, 2-(2-phenylethyloxy)-; and mixtures thereof.
• the most preferred di(hydroxyalkyl)ethers include: bis(2-hydroxybutyl)ether; and bis(2-hydroxycyclopentyl)ether;
• the alicyclic diols and their derivatives that are preferred include: (1) the saturated diols and their derivatives including: 1-isopropyl-1,2-cyclobutanediol; 3-ethyl-4-methyl-1,2-cyclobutanediol; 3-propyl-1,2-cyclobutanediol; 3-isopropyl-1,2-cyclobutanediol; 1-ethyl-1,2-cyclopentanediol; 1,2-dimethyl-1,2-cyclopentanediol; 1,4-dimethyl-1,2-cyclopentanediol; 2,4,5-trimethyl-1,3-cyclopentanediol; 3,3-dimethyl-1,2-cyclopentanediol; 3,4-dimethyl-1,2-cyclopentanediol; 3,5-dimethyl-1,2-cyclopentanediol; 3-ethyl-1,2-cyclopentanediol
• the most preferred saturated alicyclic diols and their derivatives are: 1-isopropyl-1,2-cyclobutanediol; 3-ethyl-4-methyl-1,2-cyclobutanediol; 3-propyl-1,2-cyclobutanediol; 3-isopropyl-1,2-cyclobutanediol; 1-ethyl-1,2-cyclopentanediol; 1,2-dimethyl-1,2-cyclopentanediol; 1,4-dimethyl-1,2-cyclopentanediol; 3,3-dimethyl-1,2-cyclopentanediol; 3,4-dimethyl-1,2-cyclopentanediol; 3,5-dimethyl-1,2-cyclopentanediol; 3-ethyl-1,2-cyclopentanediol; 4,4-dimethyl-1,2-cyclopentanediol; 4-ethyl-1,2-cyclopentan
• Preferred aromatic diols include: 1-phenyl-1,2-ethanediol; 1-phenyl-1,2-propanediol; 2-phenyl-1,2-propanediol; 3-phenyl-1,2-propanediol; 1-(3-methylphenyl)-1,3-propanediol; 1-(4-methylphenyl)-1,3-propanediol; 2-methyl-1-phenyl-1,3-propanediol; 1-phenyl-1,3-butanediol; 3-phenyl-1,3-butanediol; and/or 1-phenyl-1,4-butanediol, of which, 1-phenyl-1,2-propanediol; 2-phenyl-1,2-propanediol; 3-phenyl-1,2-propanediol; 1-(3-methylphenyl)-1,3-propanediol; 1-(4-
• the specific preferred unsaturated diol principal solvents are: 1,3-butanediol, 2,2-diallyl-; 1,3-butanediol, 2-(1-ethyl-1-propenyl)-; 1,3-butanediol, 2-(2-butenyl)-2-methyl-; 1,3-butanediol, 2-(3-methyl-2-butenyl)-; 1,3-butanediol, 2-ethyl-2-(2-propenyl)-; 1,3-butanediol, 2-methyl-2-(1-methyl-2-propenyl)-; 1,4-butanediol, 2,3-bis(1-methylethylidene)-;
• Said principal alcohol solvent can also preferably be selected from the group consisting of: 2,5-dimethyl-2,5-hexanediol; 2-ethyl-1,3-hexanediol; 2-methyl-2-propyl-1,3-propanediol; 1,2-hexanediol; and mixtures thereof. More preferably said principal alcohol solvent is selected from the group consisting of 2-ethyl-1,3-hexanediol; 2-methyl-2-propyl-1,3-propanediol; 1,2-hexanediol; and mixtures thereof. Even more preferably, said principal alcohol solvent is selected from the groups consisting of 2-ethyl-1,3-hexanediol; 1,2-hexanediol; and mixtures thereof.
• 2,2-Dimethyl-6-heptene-1,3-diol (CAS No. 140192-39-8) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to either of the following preferred C8-diol principal solvents: 2-methyl-1,3-heptanediol or 2,2-dimethyl-1,3-hexanediol.
• 2,4-Dimethyl-5-heptene-1,3-diol (CAS No. 123363-69-9) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to either of the following preferred C8-diol principal solvents: 2-methyl-1,3-heptanediol or 2,4-dimethyl-1,3-hexanediol.
• 2-(1-Ethyl-1-propenyl)-1,3-butanediol (CAS No. 116103-35-6) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to either of the following preferred C8-diol principal solvents: 2-(1-ethylpropyl)-1,3-propanediol or 2-(1-methylpropyl)-1,3-butanediol.
• 2-Ethenyl-3-ethyl-1,3-pentanediol (CAS No. 104683-37-6) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to either of the following preferred C8-diol principal solvents: 3-ethyl-2-methyl-1,3-pentanediol or 2-ethyl-3-methyl-1,3-pentanediol.
• 3,6-Dimethyl-5-heptene-1,4-diol (e.g., CAS No. 106777-99-5) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to any of the following preferred C8-diol principal solvents: 3-methyl-1,4-heptanediol; 6-methyl-1,4-heptanediol; or 3,5-dimethyl-1,4-hexanediol.
• 5,6-Dimethyl-6-heptene-1,4-diol is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to any of the following preferred C8-diol principal solvents: 5-methyl-1,4-heptanediol; 6-methyl-1,4-heptanediol; or 4,5-dimethyl-1,3-hexanediol.
• 4-Methyl-6-octene-3,5-diol (CAS No. 156414-25-4) is a preferred C9-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to any of the following preferred C8-diol principal solvents: 3,5-octanediol, 3-methyl-2,4-heptanediol or 4-methyl-3,5-heptanediol.
• Rosiridol (CAS No. 101391-01-9) and isorosiridol (CAS No. 149252-15-3) are two isomers of 3,7-dimethyl-2,6-octadiene-1,4-diol, and are preferred C10-diol principal solvents.
• 8-Hydroxylinalool (CAS No. 103619-06-3, 2,6-dimethyl-2,7-octadiene-1,6-diol) is a preferred C10-diol principal solvent and can be considered to be derived by appropriately adding two CH 2 groups and two double bonds to any of the following preferred C8-diol principal solvents: 2-methyl-1,5-heptanediol; 5-methyl-1,5-heptanediol; 2-methyl-1,6-heptanediol; 6-methyl-1,6-heptanediol; or 2,4-dimethyl-1,4-hexanediol.
• 2,7-Dimethyl-3,7-octadiene-2,5-diol (CAS No. 171436-39-8) is a preferred C10-diol principal solvent and can be considered to be derived by appropriately adding two CH 2 group and two double bond to any of the following preferred C8-diol principal solvents: 2,5-octanediol; 6-methyl-1,4-heptanediol; 2-methyl-2,4-heptanediol; 6-methyl-2,4-heptanediol; 2-methyl-2,5-heptanediol; 6-methyl-2,5-heptanediol; and 2,5-dimethyl-2,4-hexanediol.
• 4-Butyl-2-butene-1,4-diol (CAS No. 153943-66-9) is a preferred C8-diol principal solvent and can be considered to be derived by appropriately adding a CH 2 group and a double bond to any of the following preferred C7-diol principal solvents: 2-propyl-1,4-butanediol or 2-butyl-1,3-propanediol.
• 3,5-dimethyl-5-hexene-2,4-diol is a poor unsaturated C8 solvent, and can be considered to be derived from the following poor saturated C7 solvents: 3-methyl-2,4-hexanediol; 5-methyl-2,4-hexanediol; or 2,4-dimethyl-1,3-pentanediol; and 2,6-dimethyl-5-heptene-1,2-diol (e.g., CAS No.
• saturated principal solvents always have unsaturated analogs/homologs with the same degree of acceptability.
• the exception relates to saturated diol principal solvents having the two hydroxyl groups situated on two adjacent carbon atoms.
• inserting one, or more, CH 2 groups between the two adjacent hydroxyl groups of a poor solvent results in a higher molecular weight unsaturated homolog which is more suitable for the clear, concentrated fabric softener formulation.
• the preferred unsaturated 6,6-dimethyl-1-heptene-3,5-diol CAS No.
• the inoperable unsaturated 2,4-dimethyl-5-hexene-2,4-diol (CAS No. 87604-24-8) having no adjacent hydroxyl groups can be considered to be derived from the preferred 2,3-dimethyl-2,3-pentanediol which has adjacent hydroxyl groups.
• an inoperable unsaturated solvent having no adjacent hydroxyl groups can be considered to be derived from an inoperable solvent which has adjacent hydroxyl groups, such as the pair 4,5-dimethyl-6-hexene-1,3-diol and 3,4-dimethyl-1,2-pentanediol. Therefore, in order to deduce the formulatability of an unsaturated solvent having no adjacent hydroxyl groups, one should start from a low molecular weight saturated homolog also not having adjacent hydroxyl groups. I.e., in general, the relationship is more reliable when the distance/relationship of the two hydroxy groups is maintained. I.e., it is reliable to start from a saturated solvent with adjacent hydroxyl groups to deduce the formulatability of the higher molecular weight unsaturated homologs also having adjacent hydroxyl groups.
• the principal solvents are desirably kept to the lowest levels that are feasible in the present compositions for obtaining translucency or clarity.
• the presence of water exerts an important effect on the need for the principal solvents to achieve clarity of these compositions.
• the softener active-to-principal solvent weight ratio is preferably from about 55:45 to about 85:15, more preferably from about 60:40 to about 80:20.
• the softener active-to-principal solvent weight ratio is preferably from about 45:55 to about 70:30, more preferably from about 55:45 to about 70:30. But at high water levels of from about 70% to about 80%, the softener active-to-principal solvent weight ratio is preferably from about 30:70 to about 55:45, more preferably from about 35:65 to about 45:55. At even higher water levels, the softener to principal solvent ratios should also be even higher.
• Mixtures of the above principal solvents are particularly preferred, since one of the problems associated with large amounts of solvents is safety. Mixtures decrease the amount of any one material that is present. Odor and flammability can also be mimimized by use of mixtures, especially when one of the principal solvents is volatile and/or has an odor, which is more likely for low molecular weight materials.
• Suitable solvents that can be used at levels that would not be sufficient to produce a clear product are 2,2,4-trimethyl-1,3-pentane diol; the ethoxylate, diethoxylate, or triethoxylate derivatives of 2,2,4-trimethyl-1,3-pentane diol; and/or 2-ethyl-1,3-hexanediol.
• these solvents should only be used at levels that will not provide a stable, or clear product.
• Preferred mixtures are those where the majority of the solvent is one, or more, that have been identified hereinbefore as most preferred.
• the use of mixtures of solvents is also preferred, especially when one, or more, of the preferred principal solvents are solid at room temperature. In this case, the mixtures are fluid, or have lower melting points, thus improving processability of the softener compositions.
• an effective amount of the principal solvent(s) of this invention is at least greater than about 5%, preferably more than about 7%, more preferably more than about 10% of the composition, when at least about 15% of the softener active is also present.
• the substitute solvent(s) can be used at any level, but preferably about equal to, or less than, the amount of operable principal solvent, as defined hereinbefore, that is present in the fabric softener composition.
• HPHP hydroxy pivalyl hydroxy pivalate
• mixtures of these solvents with the principal solvent e.g., with the preferred 1,2-hexanediol principal solvent, wherein the 1,2-hexanediol principal solvent is present at effective levels, also provide liquid concentrated, clear fabric softener compositions.
• the principal solvent can be used to either make a composition translucent or clear, or can be used to reduce the temperature at which the composition is translucent or clear.
• the invention also comprises the method of adding the principal solvent, at the previously indicated levels, to a composition that is not translucent, or clear, or which has a temperature where instability occurs that is too high, to make the composition translucent or clear, or, when the composition is clear, e.g., at ambient temperature, or down to a specific temperature, to reduce the temperature at which instability occurs, preferably by at least about 5oC, more preferably by at least about 10oC.
• the principal advantage of the principal solvent is that it provides the maximum advantage for a given weight of solvent. It is understood that "solvent”, as used herein, refers to the effect of the principal solvent and not to its physical form at a given temperature, since some of the principal solvents are solids at ambient temperature.
• alkyl lactate esters e.g., ethyl lactate and isopropyl lactate have ClogP values within the effective range of from about 0.15 to about 0.64, and can form liquid concentrated, clear fabric softener compositions with the fabric softener actives of this invention, but need to be used at a slightly higher level than the more effective diol solvents like 1,2-hexanediol. They can also be used to substitute for part of other principal solvents of this invention to form liquid concentrated, clear fabric softener compositions. This is illustrated in Example I-C.
• the unsaturated analogs of the operable principal solvents are novel, especially the unsaturated C 7-12 diols, more preferably unsaturated C 8-10 diols, with the exception of the specifically mentioned unsaturated diols listed above in Table IX. These principal solvents all provide the unobvious benefit described hereinbefore.
• Low molecular weight water soluble solvents can also be used at levels of of from 0% to about 12%, preferably from about 1% to about 10%, more preferably from about 2% to about 8%.
• the water soluble solvents cannot provide a clear product at the same low levels of the principal solvents described hereinbefore but can provide clear product when the principal solvent is not sufficient to provide completely clear product. The presence of these water soluble solvents is therefore highly desirable.
• Such solvents include: ethanol; isopropanol; 1,2-propanediol; 1,3-propanediol; propylene carbonate; etc. but do not include any of the principal solvents (B).
• These water soluble solvents have a greater affinity for water in the presence of hydrophobic materials like the softener active than the principal solvents.
• compositions herein can also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.001% to 1% by weight of such optical brighteners.
• hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
• R 1 is anilino
• R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
• the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
• This particular brightener species is, commercially marketed under the tradename Tinopal-UNPA-GX® by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.
• R 1 is anilino
• R 2 is N-2-hydroxyethyl-N-2-methylamino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX® by Ciba-Geigy Corporation.
• R 1 is anilino
• R 2 is morphilino
• M is a cation such as sodium
• the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
• This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX® by Ciba Geigy Corporation.
• compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids.
• the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients.
• concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used.
• the surfactant concentration aids are typically selected from the group consisting of (1) single long chain alkyl cationic surfactants; (2) nonionic surfactants; (3) amine oxides; (4) fatty acids; and (5) mixtures thereof.
• the total level is from about 2% to about 25%, preferably from about 3% to about 17%, more preferably from about 4% to about 15%, and even more preferably from 5% to about 13% by weight of the composition.
• These materials can either be added as part of the active softener raw material, (I), e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the biodegradable fabric softener active as discussed hereinbefore, or added as a separate component.
• the total level of dispersibility aid includes any amount that may be present as part of component (I).
• the mono-alkyl cationic quaternary ammonium compound When the mono-alkyl cationic quaternary ammonium compound is present, it is typically present at a level of from about 2% to about 25%, preferably from about 3% to about 17%, more preferably from about 4% to about 15%, and even more preferably from 5% to about 13% by weight of the composition, the total mono-alkyl cationic quaternary ammonium compound being at least at an effective level.
• Such mono-alkyl cationic quaternary ammonium compounds useful in the present invention are, preferably, quaternary ammonium salts of the general formula: [R 4 N + (R 5 ) 3 ] X - wherein R 4 is C 8 -C 22 alkyl or alkenyl group, preferably C 10 -C 18 alkyl or alkenyl group; more preferably C 10 -C 14 or C 16 -C 18 alkyl or alkenyl group; each R 5 is a C 1 -C 6 alkyl or substituted alkyl group (e.g., hydroxy alkyl), preferably C 1 -C 3 alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, a benzyl group, hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene units, preferably from about 2.5 to about 13 oxyethylene units, more preferably from about 3 to about 10 oxyethylene units,
• Especially preferred dispersibility aids are monolauryl trimethyl ammonium chloride and monotallow trimethyl ammonium chloride available from Witco under the trade name Varisoft® 471 and monooleyl trimethyl ammonium chloride available from Witco under the tradename Varisoft® 417.
• the R 4 group can also be attached to the cationic nitrogen atom through a group containing one, or more, ester, amide, ether, amine, etc., linking groups which can be desirable for increased concentratability of component (I), etc.
• Such linking groups are preferably within from about one to about three carbon atoms of the nitrogen atom.
• Mono-alkyl cationic quaternary ammonium compounds also include C 8 -C 22 alkyl choline esters.
• the preferred dispersibility aids of this type have the formula: R 1 C(O)-O-CH 2 CH 2 N + (R) 3 X - wherein R 1 , R and X - are as defined previously.
• Highly preferred dispersibility aids include C 12 -C 14 coco choline ester and C 16 -C 18 tallow choline ester.
• the compositions also contain a small amount, preferably from about 2% to about 5% by weight of the composition, of organic acid.
• organic acids are described in European Patent Application No. 404,471, Machin et al., published on Dec. 27, 1990, supra, which is herein incorporated by reference.
• the organic acid is selected from the group consisting of glycolic acid, acetic acid, citric acid, and mixtures thereof.
• Ethoxylated quaternary ammonium compounds which can serve as the dispersibility aid include ethylbis(polyethoxy ethanol)alkylammonium ethyl-sulfate with 17 moles of ethylene oxide, available under the trade name Variquat® 66 from Sherex Chemical Company; polyethylene glycol (15) oleammonium chloride, available under the trade name Ethoquad® 0/25 from Akzo; and polyethylene glycol (15) cocomonium chloride, available under the trade name Ethoquad® C/25 from Akzo.
• the dispersibility aid is to increase the dispersibility of the ester softener
• the dispersibility aids of the present invention also have some softening properties to boost softening performance of the composition. Therefore, preferably the compositions of the present invention are essentially free of non-nitrogenous ethoxylated nonionic dispersibility aids which will decrease the overall softening performance of the compositions.
• quaternary compounds having only a single long alkyl chain can protect the cationic softener from interacting with anionic surfactants and/or detergent builders that are carried over into the rinse from the wash solution.
• Suitable amine oxides include those with one alkyl or hydroxyalkyl moiety of about 8 to about 22 carbon atoms, preferably from about 10 to about 18 carbon atoms, more preferably from about 8 to about 14 carbon atoms, and two alkyl moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups with about 1 to about 3 carbon atoms.
• Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecyl-amine oxide, dimethyldodecylamine oxide, dipropyl-tetradecylamine oxide, methylethylhexadecylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyl dimethylamine oxide.
• Stabilizers can be present in the compositions of the present invention.
• the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.035% to about 0.1% for antioxidants, and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions. Antioxidants and reductive agent stabilizers are especially critical for unscented or low scent products (no or low perfume).
• antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox® S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox®-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox® GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C 8 -C 22 ) of gallic acid, e.g., do
• an optional soil release agent can be added.
• the addition of the soil release agent can occur in combination with the premix, in combination with the acid/water seat, before or after electrolyte addition, or after the final composition is made.
• the softening composition prepared by the process of the present invention herein can contain from 0% to about 10%, preferably from 0.2% to about 5%, of a soil release agent.
• a soil release agent is a polymer.
• Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.
• a preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 5,000 to about 55,000.
• Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
• this polymer include the commercially available materials Zelcon 4780® (from Dupont) and Milease T® (from ICI).
• Highly preferred soil release agents are polymers of the generic formula: in which each X can be a suitable capping group, with each X typically being selected from the group consisting of H, and alkyl or acyl groups containing from about 1 to about 4 carbon atoms.
• p is selected for water solubility and generally is from about 6 to about 113, preferably from about 20 to about 50.
• u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore, there should be at least 20%, preferably at least 40%, of material in which u ranges from about 3 to about 5.
• the R 14 moieties are essentially 1,4-phenylene moieties.
• the term "the R 14 moieties are essentially 1,4-phenylene moieties” refers to compounds where the R 14 moieties consist entirely of 1,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkenyl moieties, alkenylene moieties, or mixtures thereof.
• Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene, and mixtures thereof.
• Alkylene and alkenylene moieties which can be partially substituted include 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
• the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent.
• the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
• compounds where the R 14 comprise from about 50% to about 100% 1,4-phenylene moieties (from 0% to about 50% moieties other than 1,4-phenylene) have adequate soil release activity.
• polyesters made according to the present invention with a 40:60 mole ratio of isophthalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity.
• the R 14 moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e., each R 14 moiety is 1,4-phenylene.
• suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene, and mixtures thereof.
• the R 15 moieties are essentially ethylene moieties, 1,2-propylene moieties, or mixtures thereof. Inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of compounds.
• 1,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the soil release component in the liquid fabric softener compositions.
• each p is at least about 6, and preferably is at least about 10.
• the value for each n usually ranges from about 12 to about 113. Typically the value for each p is in the range of from about 12 to about 43.
• soil release agents can also act as scum dispersants.
• the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting point(s) of the components.
• the preferred scum dispersants herein are formed by highly ethoxylating hydrophobic materials.
• the hydrophobic material can be a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxide, quaternary ammonium compound, or the hydrophobic moieties used to form soil release polymers.
• the preferred scum dispersants are highly ethoxylated, e.g., more than about 17, preferably more than about 25, more preferably more than about 40, moles of ethylene oxide per molecule on the average, with the polyethylene oxide portion being from about 76% to about 97%, preferably from about 81% to about 94%, of the total molecular weight.
• the level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent.
• the amount of anionic or nonionic detergent, etc., used in the wash cycle of a typical laundering process the efficiency of the rinsing steps prior to the introduction of the compositions herein, and the water hardness, the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary.
• the minimum amount of scum dispersant should be used to avoid adversely affecting softening properties.
• scum dispersion requires at least about 2%, preferably at least about 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active.
• levels of about 10% (relative to the softener material) or more one risks loss of softening efficacy of the product especially when the fabrics contain high proportions of nonionic surfactant which has been absorbed during the washing operation.
• Preferred scum dispersants are: Brij 700®; Varonic U-250®; Genapol T-500 ®, Genapol T-800®; Plurafac A-79®; and Neodol 25-50®.
• bactericides used in the compositions of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located in Philadelphia, Pennsylvania, under the trade name Bronopol®, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under the trade name Kathon about 1 to about 1,000 ppm by weight of the agent.
• the present invention can contain any softener compatible perfume. Suitable perfumes are disclosed in U.S. Pat. 5,500,138, Bacon et al., issued March 19, 1996, said patent being incorporated herein by reference.
• perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
• natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
• artificial i.e., a mixture of different nature oils or oil constituents
• synthetic i.e., synthetically produced
• perfumes are complex mixtures of a plurality of organic compounds.
• perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl- cis -2,6-octadien-1-ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl- trans -2,6-octadien-1-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbox
• fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma; methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol methylether; methyl-beta-naphthylketone; coumarin; decylaldehyde; benzaldehyde; 4-tert-butylcyclohexyl acetate; alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl acetate; Schiff's base of 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; i
• perfume components are geraniol; geranyl acetate; linalool; linalyl acetate; tetrahydrolinalool; citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol; benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate; vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal; 2-methyl-3-(
• the perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
• Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.
• the amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
• Perfume can be present at a level of from 0% to about 10%, preferably from about 0.1% to about 5%, and more preferably from about 0.2% to about 3%, by weight of the finished composition.
• Fabric softener compositions of the present invention provide improved fabric perfume deposition.
• compositions and processes herein can optionally employ one or more copper and/or nickel chelating agents ("chelators").
• chelators can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined.
• the whiteness and/or brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved.
• Amino carboxylates useful as chelating agents herein include ethylenediaminetetraacetates (EDTA), N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates (NTA), ethylenediamine tetraproprionates, ethylenediamine-N,N'-diglutamates, 2-hyroxypropylenediamine-N,N'-disuccinates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates (DETPA), and ethanoldiglycines, including their water-soluble salts such as the alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
• EDTA ethylenediaminetetraacetates
• NDA nitrilotriacetates
• ethylenediamine tetraproprionates ethylenediamine-N,N'-diglutamates
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), diethylenetriamine-N,N,N',N",N"-pentakis(methane phosphonate) (DETMP) and 1-hydroxyethane-1,1-diphosphonate (HEDP).
• these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• the chelating agents are typically used in the present rinse process at levels from about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours' soaking.
• the preferred EDDS chelator used herein (also known as ethylenediamine-N,N'-disuccinate) is the material described in U.S. Patent 4,704,233, cited hereinabove, and has the formula (shown in free acid form):
• EDDS can be prepared using maleic anhydride and ethylenediamine.
• the preferred biodegradable [S,S] isomer of EDDS can be prepared by reacting L-aspartic acid with 1,2-dibromoethane.
• the EDDS has advantages over other chelators in that it is effective for chelating both copper and nickel cations, is available in a biodegradable form, and does not contain phosphorus.
• the EDDS employed herein as a chelator is typically in its salt form, i.e., wherein one or more of the four acidic hydrogens are replaced by a water-soluble cation M, such as sodium, potassium, ammonium, triethanolammonium, and the like.
• the EDDS chelator is also typically used in the present rinse process at levels from about 2 ppm to about 25 ppm for periods from 1 minute up to several hours' soaking. At certain pH's the EDDS is preferably used in combination with zinc cations.
• chelators can be used herein. Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like, can also be used, although such chelators are not as effective as the amino carboxylates and phosphonates, on a weight basis. Accordingly, usage levels may be adjusted to take into account differing degrees of chelating effectiveness.
• the chelators herein will preferably have a stability constant (of the fully ionized chelator) for copper ions of at least about 5, preferably at least about 7. Typically, the chelators will comprise from about 0.5% to about 10%, more preferably from about 0.75% to about 5%, by weight of the compositions herein, in addition to those that are stabilizers.
• Preferred chelators include DETMP, DETPA, NTA, EDDS and mixtures thereof.
• the present invention can include optional components conventionally used in textile treatment compositions, for example: colorants; preservatives; surfactants; anti-shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; antioxidants such as butylated hydroxy toluene, anti-corrosion agents, and the like.
• Particularly preferred ingredients include water soluble calcium and/or magnesium compounds, which provide additional stability.
• the chloride salts are preferred, but acetate, nitrate, etc. salts can be used.
• the level of said calcium and/or magnesium salts is from 0% to about 2%, preferably from about 0.05% to about 0.5%, more preferably from about 0.1% to about 0.25%.
• the present invention can also include other compatible ingredients, including those as disclosed in copending applications Serial Nos.: 08/372,068, filed January 12, 1995, Rusche, et al.; 08/372,490, filed January 12, 1995, Shaw, et al.; and 08/277,558, filed July 19, 1994, Hartman, et al., incorporated herein by reference.
• This synthesis method is a general preparation of ⁇ , ⁇ -type diols derived from substituted cyclic alkenes.
• cyclic alkenes are the alkylated isomers of cyclopentene, cyclohexene, and cycloheptene.
• the general formula of useful alkylated cyclic alkenes is wherein each R is H, or C 1 -C 4 -alkyl, and where x is 3, 4, or 5.
• Cyclic alkenes may be converted to the terminal diols by a three step reaction sequence.
• Step 1 is the reaction of the cyclic alkene with ozone (O 3 ) in a solvent such as anhydrous ethyl acetate to form the intermediate ozonide.
• Step 2 the ozonide is reduced by, e.g., palladium catalyst /H 2 to the dialdehyde which is then converted in Step 3 to the target diol by borohydride reduction.
• the 1,2- diols are generally prepared by direct hydroxylation of the appropriate substituted olefins.
• the alkene is reacted with hydrogen peroxide (30%) and a catalytic amount of osmium tetroxide in t-butyl alcohol or other suitable solvent.
• the reaction is cooled to about 0°C and allowed to run overnight. Unreacted compounds and solvent are removed by distillation and the desired 1,2- diol isolated by distillation or crystallization.
• An alternate method is the conversion of the olefin to the epoxide by the reaction of m-chloroperbenzoic acid, or peracetic acid, in a solvent such as methylene chloride at temperatures below about 25°C.
• the epoxide generated by this chemistry is then opened to the diol by, e.g., hydrolysis with dilute sulfuric acid. Step 3 to the target diol by borohydride reduction.
• This preparation is for the general type of 1,3-diols and accommodates a variety of structural features.
• Enamines are formed from both ketones and aldehydes which react with acid chlorides to form the acylated product.
• the acylated amine derivative is hydrolyzed back to its acylated carbonyl compound which is the 1,3-dicarbonyl precursor to the desired 1,3-diol.
• the diol is generated by borohydride reduction of the 1,3-dicarbonyl compound.
• acetaldehyde may be reacted with a secondary amine, preferably cyclic amines such as pyrrolidine or morpholine, by heating at reflux in a solvent such as toluene and with a catalytic amount of p-toluene sulfonic acid.
• a secondary amine preferably cyclic amines such as pyrrolidine or morpholine
• water is produced and is removed, e.g., by reflux through a water trap.
• the reaction mixture is stripped, e.g., under vacuum, to remove the solvent, if desired (the acylation can be done in the same solvent systems in most cases).
• the anhydrous crude enamine containing some excess amine is reacted with the appropriate acid chloride at about 20°C to give the acylated enamine.
• This reaction is usually allowed to stir overnight at room temperature.
• the total reaction mixture is then poured over crushed ice, stirred, and the mixture made acidic with 20% HCI.
• This treatment hydrolyzes the enamine to the acylated dicarbonyl compound.
• This intermediate is then isolated by extraction and distillation to remove low boiling impurities, then reduced by sodium borohydride to the desired 1,3- diol.
• the typical reactions involve one or more aldehydes, one or more ketones, and mixtures thereof, which have at least one alpha-hydrogen atom on the carbon atom next to the carbonyl group.
• Typical examples of some reactants and some potential final products are as follows 2 R-CH 2 -CHO ⁇ HO-CH 2 -CH(R)-CHOH-CH 2 -R R-CH 2 -CHO + R'-CH 2 -CHO ⁇ HO-CH 2 -CH(R)-CHOH-CH 2 -R + HO-CH 2 -CH(R')-CHOH-CH 2 -R' + HO-CH 2 -CH(R')-CHOH-CH 2 -R + HO-CH 2 -CH(R)-CHOH-CH 2 -R' R-CH 2 -CHO + R'-CO-CH 3 ⁇ HO-CH 2 -CH(R)-CHOH-CH 2 -R + R-CH 2 -CHOH CH 2 -CHOH-
• the aldehyde, ketone, or mixture thereof which is to be condensed is placed in an autoclave under an inert atmosphere with a solvent such as butanol or with a phase transfer medium such as polyethylene glycol.
• a mixed condensation such as with a ketone and an aldehyde is the target, typically the two reactants are used in about 1:1 mole ratio.
• a catalytic amount of strongly alkaline catalyst such as sodium methoxide is added, typically about 0.5-10 mole% of the reactants.
• the autoclave is sealed, and the mixture is heated at about 35-100°C until most of the original reactants have been converted, usually about 5 minutes to about 3 hours.
• the crude mixture is neutralized and the carbonyl functions present are reduced by hydrogenation over Raney Ni at about 100°C and about 50 atm for about 1 hour. Volatile components are removed by distillation and the desired diol principal solvents are obtained by vacuum distiiiation.
• n-butanol about 148 g, about 2 mole, Aldrich
• sodium metal about 2.3 g, about 0.1 mole, Aldrich
• a mixture of butyraldehyde (about 72 g, about 1 mole, Aldrich) and isobutyraldehyde (about 72 g, about 1 mole, Aldrich) is added and the system is held at about 40°C until most of the original aldehydes have undergone reaction.
• the base catalyst is neutralized by careful addition of sulfuric acid, any salts are removed by filtration, and the solution is hydrogenated over Raney Ni at about 100°C at about 50 atm of pressure for about 1 hour to yield a mixture of 8-carbon,1,3-diols.
• the butanol solvent and any isobutanol formed during the hydrogenation are removed by distillation to yield the eight-carbon-1,3-diol mixture of: 2,2,4-trimethyl-1,3-pentanediol; 2-ethyl-1,3-hexanediol; 2,2-dimethyl-1,3-hexanediol; and 2-ethyl-4-methyl-1,3-pentanediol.
• this mixture is further purified by vacuum distillation, or by decolorization with activated charcoal.
• the recovered solvent is used for further batches of diol production.
• the mixtures prepared by the condensation of butyraldehyde, isobutyraldehyde, and/or methyl ethyl ketone preferably have no more than about 90%, preferably no more than about 80%, more preferably no more than about 70%, even more preferably no more than about 60%, and most preferably no more than about 50%, by weight of any one specific compound.
• the reaction mixtures should not contain more than about 95%, preferably no more than about 90%, more preferably no more than about 85%, and most preferably no more than about 80%, by weight, of butyraldehyde or isobutyraldehyde.
• Dimetallic acetylides Na + - :C ⁇ C: - Na + react with aldehydes or ketones to form unsaturated alcohols, e.g.,
• the resulting acetylenic diol is then reduced to the alkene or completely reduced to the saturated diol.
• the reaction can also be done by using an about 18% slurry of mono-sodium acetylide with the carbonyl compound to form the acetylenic alcohol which can be converted to the sodium salt and reacted with another mole of carbonyl compound to give the unsaturated 1,4- diol.
• mono-sodium acetylide with the carbonyl compound to form the acetylenic alcohol which can be converted to the sodium salt and reacted with another mole of carbonyl compound to give the unsaturated 1,4- diol.
• a sodium acetylide (about 18% in xylene) slurry is reacted with isobutryaldehyde to form the acetylenic alcohol (CH 3 ) 2 CH-CHO + NaC ⁇ CH ⁇ (CH 3 ) 2 CH-CHOH-C ⁇ C-H
• the acetylenic (ethynyl) alcohol is converted with base to the sodium acetylide R-CHOH-C ⁇ CNa which is then reacted with a mole of acetaldehyde to give the ethynyl diol R-CHOH-C ⁇ C-CHOH-R'.
• This compound, (CH 3 ) 2 CH-CHOH-C ⁇ C-CHOH-CH3 can be isolated as the unsaturated diol, if desired, reduced by catalytic hydrogenation to the corresponding material containing a double bond in place of the acetylenic bond, or further reduced by catalytic hydrogenation to the saturated 1,4-diol.
• This method of preparation is for the synthesis of diols, especially several 1,4-diols, which are derived from dicarboxylic acid anhydrides, diesters and lactones, but not limited to the 1,4-diols or four-carbon diacids.
• diols are generally synthesized by the reduction of the parent anhydride, lactone or diester with sodium bis(2-methoxyethoxy)aluminum hydride (Red-AI) as the reducing agent.
• This reducing agent is commercially available as a 3.1 molar solution in toluene and delivers one mole of hydrogen per mole of reagent.
• Diesters and cyclic anhydrides require about 3 moles of Red-Al per mole of substrate.
• the typical reduction is carried out as follows.
• the anhydride is first dissolved in anhydrous toluene and placed in a reaction vessel equipped with dropping funnel, mechanical stirrer, thermometer and a reflux condenser connected to calcium chloride and soda lime tubes to exclude moisture and carbon dioxide.
• the reducing agent, in toluene is placed in the dropping funnel and is added slowly to the stirred anhydride solution.
• the reaction is exothermic and the temperature is allowed to reach about 80oC. It is maintained at about 80oC during the remaining addition time and for about two hours following addition.
• reaction mixture is then allowed to cool back to room temperature.
• the mixture is added to a stirred aqueous HCI solution (about 20% concentration) which is cooled in an ice bath, and the temperature is maintained at about 20 to 30oC.
• acidification the mixture is separated in a separatory funnel and the organic layer washed with a dilute salt solution until neutral to pH paper.
• the neutral diol solution is dried over anhydrous magnesium sulfate, filtered, then stripped under vacuum to yield the desired 1,4-diol.
• This method is a general preparation of some 1,3-, 1,4- and 1,5-diols which utilizes the chemistry outlined in Method A-1 and Method A-2.
• the variation here is the use of a cyclic alkadienes in place of the cycloalkenes described in Methods A.
• the general formula for the starting materials is wherein each R is H, or C 1 -C 4 -alkyl and wherein x is 1, 2 or 3.
• the reactions are those of Methods A with the variation of having one mole of ethylene glycol generated for each mole of the desired diol principal solvent formed, e.g., the following preparation of 2,2-dimethyl-1,4-haxanediol from 1-ethyl-5,5-dimethyl-1,3-cyclohexanediol (CAS No. 79419-18-4):
• the polyethoxylated derivatives of diol principal solvents are typically prepared in a high-pressure reactor under a nitrogen atmosphere.
• a suitable amount of ethylene oxide is added to a mixture of a diol solvent and potassium hydroxide at high temperature (from about 80oC to about 170oC).
• the amount of ethylene oxide is calculated relative to the amount of the diol solvent in order to add the right number of ethylene oxide groups per molecule of diol.
• Methyl-capped polyethoxylated derivatives of diols are typically prepared either by reacting a methoxypoly(ethoxy)ethyl chloride (i.e., CH 3 O-(CH 2 CH 2 O) n -CH 2 CH 2 -Cl) of the desired chain length with the selected diol, or by reacting a methyl-capped polyethylene glycol (i.e., CH 3 O-(CH 2 CH 2 O) n -CH 2 CH 2 -OH) of the desired chain length with the epoxy precursor of the diol, or a combination of these methods.
• a methoxypoly(ethoxy)ethyl chloride i.e., CH 3 O-(CH 2 CH 2 O) n -CH 2 CH 2 -Cl
• a methyl-capped polyethylene glycol i.e., CH 3 O-(CH 2 CH 2 O) n -CH 2 CH 2 -OH
• reaction mixture is cooled, poured into an equal volume of water, neutralized with 6 N HCI, saturated with sodium chloride, and extracted twice with dichloromethane.
• dichloromethane layers are dried over sodium sulfate and solvent is stripped to yield the desired polyether alcohol in crude form,
• purification is accomplished by fractional vacuum distillation.
• Saturated sodium chloride solution is slowly added to the material until the thionyl chloride is destroyed.
• the material is taken up in about 300 ml of saturated sodium chloride solution and extracted with about 500 ml of methylene chloride.
• the organic layer is dried and solvent is stripped on a rotary evaporator to yield crude methoxyethoxyethyl chloride.
• purification is accomplished by fractional vacuum distillation.
• the alcohol C 2 H 5 CH(OH)CH(CH 3 )CH 2 OH (about 116 grams, about 1.0 mole), is placed in a 1-liter, three-neck round bottom flask equipped with a magnetic stirring bar, condenser, and temperature controller (Thermowatch®, I 2 R) along with about 100 ml of tetrahydrofuran as solvent.
• sodium hydride about 32 grams, about 1.24 moles
• Methoxytriethoxyethyl chloride about 242 grams, about 1.2 moles, prepared as above is added and the system is held at reflux for about 48 hours.
• the reaction mixture is cooled to room temperature and water is cautiously added dropwise with stirring to decompose excess hydride.
• the tetrahydrofuran is stripped off on a rotary evaporator.
• the crude product is dissolved in about 400 ml of water and enough sodium chloride is dissolved in the water to bring it nearly to the saturation level.
• the mixture is then extracted twice with about 300 ml portions of dichloromethane.
• the combined dichloromethane layers are dried over sodium sulfate and the solvent is then stripped on a rotary evaporator to yield the crude product.
• purification is accomplished by further stripping of unreacted starting materials and low MW byproducts by utilizing a kugelrohr apparatus at about 150°C under vacuum.
• further purification is accomplished by vacuum distillation to yield the title polyether.
• a three neck, round bottom flask is equipped with a magnetic stir bar, a solid CO 2 -cooled condenser, an addition funnel, a thermometer, and a temperature control device (Therm-O-Watch, I2R).
• the system is swept free of air by a stream of nitrogen and then is equipped for blanketing the reaction mixture with a nitrogen atmosphere.
• To the reaction flask is added the dry alcohol or diol to be propoxylated. About 0.1-5 mole % of sodium metal is added cautiously to the reaction vessel in portions with heating if necessary to get all the sodium to react.
• the reaction mixture is then heated to about 80-130°C and propylene oxide (Aldrich) is added dropwise from the dropping funnel at a rate to maintain a small amount of relux from the solid CO 2 -cooled condenser. Addition of propylene oxide is continued until the desired amount has been added for the target degree of propoxylation. Heating is continued until all reflux of propylene oxide ceases and the temperature is maintained for about an additional hour to ensure complete reaction.
• the reaction mixture is then cooled to room temperature and is neutralized by careful addition of a convenient acid such as methanesulfonic acid. Any salts are removed by filtration to give the desired propoxylated product.
• the average degree of propoxylation is typically confirmed by integration of the 1 H-NMR spectrum.
• a three neck, round bottom flask is equipped with a magnetic stir bar, a solid CO 2 -cooled condenser, an addition funnel, a thermometer, and a temperature control device (Therm-O-Watch, I2R).
• the system is swept free of air by a stream of nitrogen and then is equipped for blanketing the reaction mixture with a nitrogen atmosphere.
• To the reaction flask is added the dry alcohol or diol to be butoxylated. About 0.1-5 mole % of sodium metal is added cautiously to the reaction vessel in portions with heating if necessary to get all the sodium to react.
• reaction mixture is then heated to about 80-130°C and ⁇ -butylene oxide (Aldrich) is added dropwise from the dropping funnel at a rate to maintain a small amount of reflux from the solid CO 2 -cooled condenser.
• Addition of butylene oxide is continued until the desired amount has been added for the target degree of butoxylation. Heating is continued until all reflux of butylene oxide ceases and the temperature is maintained for about an additional one to two hours to ensure complete reaction.
• the reaction mixture is then cooled to room temperature and is neutralized by careful addition of a convenient acid such as methanesulfonic acid. Any salts are removed by filtration to give the desired butoxylated product.
• the average degree of butoxylation is typically confirmed by integration of the 1 H-NMR spectrum.
• a dry portion of about 0.1 mole of the desired alcohol or diol starting material is placed in a 3-neck, round bottom flask equipped with magnetic stirrer, condenser, internal thermometer and an argon blanketing system. If the desired average degree of "tetramethyleneoxylation" is about one per hydroxyl group, about 0.11 moles of 2-(4-chlorobutoxy)tetrahydropyran (ICI) is added per mole of alcohol function. A solvent is added if necessary such as dry tetrahydrofuran, dioxane or dimethylformamide.
• ICI 2-(4-chlorobutoxy)tetrahydropyran
• sodium hydride (about 5 mole % excess relative to the chloro compound) is added in small portions with good stirring while maintaining a temperature of about 30-120°C After all the hydride has reacted, the temperature is maintained until all of the alcohol groups have been alkylated, usually about 4-24 hours. After the reaction is complete, it is cooled and the excess hydride is decomposed by careful addition of methanol in small portions. Then about an equal volume of water is added and the pH is adjusted to about 2 with sulfuric acid. After warming to about 40°C and holding it there for about 15 minutes to hydrolyze the tetrahydropyranyl protecting group, the reaction mixture is neutralized with sodium hydroxide and the solvents are stripped on a rotary evaporator.
• the residue is taken up in ether or methylene chloride and salts are removed by filtration. Stripping yields the crude tetramethyleneoxylated alcohol or diol. Further purification may be accomplished by vacuum distillation. If a final average degree of tetramethyleneoxylation of less than one is desired, a correspondingly lesser amount of chloro compound and hydride are used. For average degrees of tetramethyleneoxylation greater than one, the entire process is repeated in cycles until the buildup reaches the target level.
• a convenient method to prepare alkyl and/or aryl monoglycerol ethers consists of first preparing the corresponding alkyl glycidyl ether precursor. This is then converted to a ketal, which is then hydrolyzed to the monoglyceryl ether (diol). Following is the illustrative example of the preparation of the preferred n-pentyl monoglycerol ether, (i.e., 3-(pentyloxy)-1,2-propanediol) n-C 5 H 11 -O-CHOH-CH 2 OH.
• a 3-neck, 2-liter round bottomed reaction flask (equipped with overhead stirrer, cold water condenser, mercury thermometer and addition funnel) are charged with about 546 g of aqueous NaOH (about 50% concentration) and about 38.5 g of tetrabutylammonium hydrogen sulfate (PTC, phase transfer catalyst). The content of the flask is stirred to achieve dissolution and then about 200 g of 1-pentanol is added along with about 400 mi hexanes (a mixture of isomers, with about 85% n-hexane). Into the addition funnel is charged about 418 g of epichlorohydrin which is slowly added (dropwise) to the stirring reaction mix. The temperature gradually rises to about 68oC due to the reaction exotherm. The reaction is allowed to continue for about 1 hr after complete addition of the epichlorohydrin (no additional heat).
• PTC tetrabutylammonium hydrogen sulfate
• the crude reaction mix is diluted with about 500 ml of warm water, stirred gently and then the aqueous layer is settled and removed.
• the hexane layer is mixed diluted again with about 1 liter of warm water and the pH of the mix is adjusted to about 6.5 by the addition of dilute aqueous sulfuric acid.
• the water layer is again separated and discarded and the hexane layer is then washed 3 times with fresh water.
• the hexane layer is then separated and evaporated to dryness via a rotary evaporator to obtain the crude n-pentyl glycidyl ether.
• a 3-neck, 2 liter round bottomed flask (equipped with an overhead stirrer, cold water condenser, mercury thermometer and addition funnel) is charged with about 1 liter of acetone.
• To the acetone is added about 1 ml of SnCl 4 with stirring.
• Into an addition funnel positioned over the reaction flask is added about 200 g of the just prepared n-pentyl glycidyl ether.
• the glycidyl ether is added very slowly to the stirring acetone solution (the rate is adjusted to control the exotherm).
• the reaction is allowed to proceed for about 1 hr after complete addition of the glycidyl ether (maximum temperature about 52oC).
• the apparatus is converted for distillation and a heating mantle and temperature controller are added.
• the crude reaction mix is concentrated via distillation of about 600 ml of acetone.
• To the cooled concentrated solution are added about 1 liter of aqueous sulfuric acid (about 20% concentration) and about 500 ml of hexanes.
• the content of the flask is then heated to about 50oC with stirring (the apparatus is adjusted to collect and separate the liberated acetone).
• the hydrolysis reaction is continued until TLC (Thin Layer Chromatography) analysis confirms the completion of reaction.
• the crude reaction mix is cooled and the aqueous layer is separated and discarded.
• the organic layer is then diluted with about 1 liter of warm water and the pH is adjusted to about 7 by the addition of dilute aqueous NaOH (1 N).
• the aqueous layer is again separated and the organic phase is washed 3 times with fresh water.
• the organic phase is then separated and evaporated via a rotary evaporator.
• the residue is then diluted with fresh hexanes and the desired product is extracted into methanol/water solution (about 70/30 weight ratio).
• the methanol/water solution is again evaporated to dryness via a rotary evaporator (with additional methanol added to facilitate the water evaporation).
• the residue is then filtered hot through glass microfiber filter paper to obtain the n-pentyl monoglycerol ether.
• reaction mixture is neutralized with sulfuric acid, the salts are removed by filtration, and the liquid is fractionally distilled under vacuum to recover the excess butanediol.
• the desired ether is obtained as a residue.
• it is purified by further vacuum distillation.
• compositions in the Examples below are made by first preparing an oil seat of DEQA softener active at ambient temperature.
• the softener active can be heated to melting at, e.g., about 130-150°F (about 55-66°C), if the softener active is not fluid at room temperature.
• the softener active is mixed using an IKA RW 25® mixer for about 2 to about 5 minutes at about 150 rpm.
• an acid/water seat is prepared by mixing the HCI with deionized (Dl) water at ambient temperature.
• the acid/water seat should also be heated to a suitable temperature, e.g., about 100oF (about 38oC) and maintaining said temperature with a water bath.
• the principal solvent(s) melted at suitable temperatures if their melting points are above room temperature
• the acid/water seat is then added to the softener premix and mixed for about 20 to about 30 minutes or until the composition is clear and homogeneous.
• the composition is allowed to air cool to ambient temperature.
• ClogP values of 2-ethyl-1,3-hexanediol and 1,2-hexanediol are 0.60 and 0.53, respectively, and are within the preferred ClogP range.
• Example IA All 1,2-alkanediols in Example IA, except 1,2-hexanediol, have ClogP values outside the effective 0.15 to 0.64 range. Only the composition of Example I-8, containing 1,2-hexanediol, is a clear composition with acceptable viscosities both at room temperature and at about 40oF (about 4oC); compositions of Comparative Examples I-8A to I-8F are not clear and/or do not have acceptable viscosities.
• Example IB All hexanediol isomers in Example IB, except 1,2-hexanediol, have ClogP values outside the effective 0.15 to 0.64 range. Only the composition of Example 1-8, containing 1,2-hexanediol, is a clear composition with acceptable viscosities both at room temperature and at about 40oF (about 4oC); compositions of Comparative Examples I-8G to I-8L are not clear and/or do not have acceptable viscosities.
• compositions of Example I-8, I-8M, and I-8N which contain effective levels of the preferred 1,2-hexanediol principal solvent are clear compositions with acceptable viscosities both at room temperature and at about 40oF (about 4oC).
• the compositions of Example I-80 and I-8P which contain effective levels of the preferred 1,2-hexanediol principal solvent are clear compositions with acceptable viscosities at room temperature, and are clear at about 40oF (about 4oC) with a small layer which is separated on top, but recover and become clear when brought back to room temperature.
• the compositions of Comparative Examples I-8Q which does not contain an effective amount of the preferred 1,2-hexanediol is not clear and/or does not have acceptable viscosities.
• 3-(n-Pentyloxy)-1,2-propanediol has a ClogP of 0.54, which is within the preferred range of 0.40 to 0.60, and all other 1,2-propanediol derivatives in Example XXXIIA have ClogP values outside the effective 0.15 to 0.64 range.
• Only the composition of Example XXXII-7, which contains 3-(n-pentyloxy)-1,2-propanediol is a clear composition with acceptable viscosities both at room temperature and at about 40oF (about 4oC); compositions of Comparative Examples XXXII-7A to XXXII-7F are not clear and/or do not have acceptable viscosities.
• Cis-1,2-bis(hydroxymethyl)cyclohexane has a ClogP of 0.47, which is within the preferred range of 0.40 to 0.60.
• 1,4-Bis(hydroxymethyl)cyclohexane also has a ClogP of 0.47, which is within the preferred range of 0.40 to 0.60, but has a center of symmetry, and does not form an acceptable composition (Composition XXXVA-5A).
• 1,2-cyclohexanediol and 4,5-dimethyl-1,2-cyclohexanediol have ClogP values which are outside the effective range of 0.15-0.64.
• Example XXXVA-5 is a clear composition with acceptable viscosities both at room temperature and at about 40oF (about 4oC); compositions of Comparative Examples XXXVA-5A to XXXVA-5C are not clear and/or do not have acceptable viscosities.
• DEQA 9 1,2-Di(oleoyloxy)-3-trimethylammoniopropane chloride wherein the acyl group is the same as that of DEQA 5 , about 88% active in ethanol.
• Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. Bal. DEQA 15 N,N-di(acyloxyethyl)-N,N-dimethyl ammonium chloride, wherein acyl group is derived from a mixture of partially hydrogenated soya fatty acid (fatty acid of DEQA 10 ) and slightly hydrogenated tallow fatty acid (fatty acid of DEQA 11 ) at an approximate 65:35 weight ratio.
• DEQA 16 N,N-di(acyloxyethyl)-N,N-dimethyl ammonium chloride, wherein acyl group is derived from a mixture of fatty acid of DEQA 1 and isostearic acid of DEQA 12 at an approximate 65:35 weight ratio.
• R 1 is a long chain C 5 -C 21 (or C 6 -C 22 ), preferably C 10 -C 20 (or C 9 -C 19 ) branched alkyl or unsaturated alkyl, most preferably C 12 -C 18 (or C 11 -C 17 ) branched alkyl and unsaturated alkyl
• the ratio of branched alkyl to unsaturated alkyl is preferably from about 95:5 to about 5:95, more preferably from about 75:25 to about 25:75, and even more preferably from about 50:50 to about 30:70
• the Iodine Value of the parent fatty acid of this R 1 group is preferably from about 20 to about 140, more preferably from about 50 to about 130; and most preferably from about 70 to about 115.
• the principal solvents B. and some mixtures of principal solvents B. and secondary solvents, as disclosed hereinbefore, allow the preparation of premixes comprising the softener active A. (from about 55% to about 85%, preferably from about 60% to about 80%, more preferably from about 65% to about 75%, by weight of the premix); the principal solvent B. (from about 10% to about 30%, preferably from about 13% to about 25%, more preferably from about 15% to about 20%, by weight of the premix); and optionally, the water soluble solvent C (from about 5% to about 20%, preferably from about 5% to about 17%, more preferably from about 5% to about 15%, by weight of the premix).
• premixes can optionally be replaced by a mixture of an effective amount of principal solvents B. and some inoperable solvents, as disclosed hereinbefore.
• These premixes contain the desired amount of fabric softening active A. and sufficient principal solvent B., and, optionally, solvent C., to give the premix the desired viscosity for the desired temperature range.
• Typical viscosities suitable for processing are less than about 1000 cps, preferably less than about 500 cps, more preferably less than about 300 cps.
• Use of low temperatures improves safety, by minimizing solvent vaporization, minimizes the degradation and/or loss of materials such as the biodegradable fabric softener active, perfumes, etc., and reduces the need for heating, thus saving on the expenses for processing.
• Additional protection for the softener active can be provided by adding, e.g., chelant such as ethylenediaminepentaacetic acid, during preparation of the active. The result is improved environmental impact and safety from the manufacturing operation.
• premixes and processes using them include premixes which typically contain from about 55% to about 85%, preferably from about 60% to about 80%, more preferably from about 65% to about 75%, of fabric softener active A., as exemplified with DEQA 1 and DEQA 8 in the Examples hereinafter, mixed with from about 10% to about 30%, preferably from about 13% to about 25%, more preferably from about 15% to about 20%, of principal solvent such as 1,2-hexanediol, and from about 5% to about 20%, preferably from about 5% to about 15%, of water soluble solvent C. like ethanol and/or isopropanol.
• principal solvent such as 1,2-hexanediol
• water soluble solvent C like ethanol and/or isopropanol.
• premixes can be used to formulate finished compositions in processes comprising the steps of:
• the fabric softening actives (DEQAs); the principal solvents B.; and, optionally, the water soluble solvents, can be formulated as premixes which can be used to prepare the following compositions.
• the above compositions are introduced into containers, specifically bottles, and more specifically clear bottles (although translucent bottles can be used), made from polypropylene (although glass, oriented polyethylene, etc., can be substituted), the bottle having a light blue tint to compensate for any yellow color that is present, or that may develop during storage (although, for short times, and perfectly clear products, clear containers with no tint, or other tints, can be used), and having an ultraviolet light absorber in the bottle to minimize the effects of ultraviolet light on the materials inside, especially the highly unsaturated actives (the absorbers can also be on the surface).
• the overall effect of the clarity and the container being to demonstrate the clarity of the compositions, thus assuring the consumer of the quality of the product.

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Citations (10)

• 1996
  • 1996-07-11 CA CA002438655A patent/CA2438655A1/fr not_active Abandoned
  • 1996-07-11 EP EP03004403A patent/EP1352948A1/fr not_active Withdrawn
  • 1996-07-24 ID IDP962101A patent/ID16311A/id unknown
  • 1996-08-19 ID IDP962369A patent/ID16312A/id unknown
• 1997
  • 1997-03-12 ZA ZA9702149A patent/ZA972149B/xx unknown

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