EP1235778A2 - Verfahren zur herstellung von etherverschlossenen poly(oxyalkylierten) alkoholtensiden - Google Patents

Verfahren zur herstellung von etherverschlossenen poly(oxyalkylierten) alkoholtensiden

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Publication number
EP1235778A2
EP1235778A2 EP00984081A EP00984081A EP1235778A2 EP 1235778 A2 EP1235778 A2 EP 1235778A2 EP 00984081 A EP00984081 A EP 00984081A EP 00984081 A EP00984081 A EP 00984081A EP 1235778 A2 EP1235778 A2 EP 1235778A2
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EP
European Patent Office
Prior art keywords
group
unsubstituted
substituted
branched
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00984081A
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English (en)
French (fr)
Inventor
Mark Robert Sivik
Glenn Thomas Jordan, Iv
Bernard William Kluesener
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP1235778A2 publication Critical patent/EP1235778A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present invention relates to a process for preparing low-foaming nonionic surfactants and more particularly to a process for preparing ether-capped poly(oxyalkylated) alcohol surfactants which have superior spotting and filming benefits in dishwashing and hard surface cleaning applications, as well as suds suppression in detergent compositions.
  • Nonionic surfactants such as alcohol ethoxylates, and alkyl glucose amides are of considerable importance in detergent products.
  • nonionic surfactants aid cleaning of greasy soils and inhibit the formation of calcium soap.
  • conventional nonionic surfactants designed for effective cleaning in laundry products form liquid crystalline phases on mixing with water. These phases can hinder the rate of mixing with water and lead to undesirable optical properties of thin films on solution drying.
  • conventional nonionics sprayed on the surface of granules to achieve target density can give rise to poor granule dissolution and residue in horizontal axis machine dispensers.
  • Conventional nonionics formulated at high levels in liquid products can lead to poor rates of mixing with water and consumer concern.
  • Conventional nonionics in window and floor cleaners can form visible liquid crystalline films on drying that increase the effort required by the consumer to achieve good results.
  • a nonionic surfactant for use in an automatic dishwashing machine would need to minimize foam production and not leave undesirable spots and films on the cleaned surfaces.
  • the need remains for new surfactants which are suitable for use in a variety of compositions which can provide improve dissolution of solid products (like bars and tablets) and granular products, improved rates of mixing with water as with liquid products, improved streaking and filming performance as in hard surface cleaners and automatic dishwashing, good cleaning, suds control and good biodegradability while avoiding incompatibility with other cleaning surfactants and/or bleach.
  • a process for preparing an ether-capped poly(oxyalkylated) alcohol surfactant has the formula: wherein, R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R 1 may be the same or different, and is independently selected from the group consisting of branched or linear C 2 to C alkylene in any given molecule; x is a number from 1 to about 30; and R 2 is selected from the group consisting of:
  • RO(R'O) x H wherein R, R 1 , and x, are as defined above;
  • novel surfactants of the present invention comprise ether-capped poly(oxyalkylated) alcohols having the formula:
  • R is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radical having from about 1 to about 20 carbon atoms, even more preferably R is a linear or branched, saturated, aliphatic hydrocarbon radicals having from about 4 to about 18 carbon atoms.
  • R, R 1 and R 2 are selected such that the ether-capped poly(oxyalkylated) alcohol surfactant contains one or more chiral carbon atoms.
  • R 2 when R 2 is (ii) then either at least one of R is other than C to C 3 alkylene or R has from 6 to 30 carbon atoms. That
  • R is either linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 6 to about 30 carbon atoms or linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms, with at least one of R 1 is other than C 2 to C alkylene.
  • R 2 is a hydrocarbon of the formula:
  • R 2 is a hydrocarbon radical of the formula:
  • R is a hydrocarbon radical of the formula: R 4 R 5 R 6
  • R ⁇ , R- ⁇ and R" are each independently selected from hydrogen, and Cj-C alkyl, , more preferably hydrogen, C1 -C2 alkyl, even more preferably hydrogen, and methyl, provided that R ⁇ , R5, and R" are not all hydrogen and, when t is 0, at least R ⁇ or R ⁇ is not hydrogen; q, r, s, t are each independently integers from 0 to 13.
  • R is selected from the formulas:
  • R is a hydrocarbon radical of the formula:
  • R 3 is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30, more preferably 1 to 20, even more preferably 1 to 15, carbon atoms,. In one embodiment of this aspect of the present invention, R 3 is ethyl.
  • R is a 4 to 8 membered substituted, or unsubstituted heterocyclic ring containing from 1 to 3 hetero atoms.
  • the hetero atoms are selected from the group comprising oxygen, nitrogen, sulfur and mixtures thereof.
  • R 2 is a 5 or 6 member heterocycle.
  • R 2 is selected from the group consisting of: wherein each R is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon or alkoxy radical having from about 1 to about 10 carbon atoms, or R 7 is a saturated or unsaturated, substituted or unsubstituted, alicyclic or aromatic hydrocarbon radical having, from about 1 to about 10 carbon atoms, which is fused to the heterocyclic ring; each A is independently selected from the group consisting of O, and N(R 8 ) a , wherein R 8 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radical having from about 1 to about 10 carbon atoms, and a is either 0 or 1 ; z is an integer from 1 to 3.
  • R 2 is selected from the group consisting of:
  • R 7 is defined as above.
  • R 2 is selected from the group consisting of: wherein R 7 and R 8 are defined as above.
  • R is a 7 to 13 membered substituted, or unsubstituted polycyclic ring.
  • R 2 is selected from the group consisting of substituted, or unsubstituted adamantane, substituted, or unsubstituted norbornane, substituted, or unsubstituted nortricyclene, and substituted, or unsubstituted bicyclo[2.2.2]octane.
  • R is a substituted, or unsubstituted adamantane.
  • R is a hydrocarbon of the formula:
  • y is an integer from 0 to 7
  • X is a 4 to 8 membered substituted, or unsubstituted, saturated or unsaturated cyclic or aromatic hydrocarbon radical.
  • y is an integer from 1 to 2
  • X is selected from the group consisting of to 5 to 8 membered substituted, or unsubstituted, aromatic hydrocarbon radical.
  • y is 0 and X, is a 5 or 6 membered substituted, or unsubstituted, saturated or unsaturated cyclic or aromatic hydrocarbon radical.
  • each R 9 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon or alkoxy radical having from about 1 to about 10 carbon atoms, or R 9 is a saturated or unsaturated, substituted or unsubstituted, alicyclic or aromatic hydrocarbon radical having, from about 1 to about 10 carbon atoms, which is fused to the ring; w is an integer from 1 to 3.
  • R is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms, more preferably R is a linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon radical having from about 1 to about 20 carbon atoms, even more preferably R 2 is a linear or branched, saturated, aliphatic hydrocarbon radicals having from about 4 to about 18 carbon atoms.
  • R 1 when x is greater than 2, R 1 may be the same or different. That is, R 1 may vary between any of the alkyleneoxy units as described above. For instance, if x is 3, R 1 may be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO);
  • the surfactants of the present invention can be prepared via a variety of different processes.
  • the surfactants may be prepared by reacting a vinyl ether of the formula:
  • R 2 OCH CH 2 wherein R is as defined above; with an alkoxylated alcohol of the formula
  • RO(R'O) x H wherein R, R 1 , and x, are as defined above, in the presence of a catalyst to form the ether- capped poly(oxyalkylated) alcohol.
  • the step of reacting of vinyl ether with alkoxylated alcohol is conducted in the presence of a catalyst.
  • Suitable catalysts include Lewis acids; acids and their salts, both organic and inorganic; pyridinium salts; polymers; clays, such as, Spanish sepiolite clay, GIRDLER K-10; aluminosilicates or zeolites, such as HZS-360 zeolite, H-Y zeolite; activated carbon, such as sulfonated charcoal; transition metal complexes, such as, molybedenyl(NI) acetylacetone; transition metal salts, such as lanthum trichloride, eerie ammonium nitrate; 2,3-dichloro-5,6,dicyano-p-benzoquinone; bis(trimethysilyl)sulfate, and mixtures thereof.
  • Suitable Lewis acids include, but are not limited to, TiCl Ti(O 1 Pr)4, ZnCl2, SnCl2, AICI3, platinum dichloride, copper(II) chloride, phosphorous pentachloride, phosphorous trichloride, cobalt(II) chloride, zinc oxide, iron(II) chloride and BF3-OEt2-
  • Suitable inorganic acids include, mineral acids, such as, phosphoric acid, sulfuric acid, hydrochloric acid, phosphorous oxychloride, aluminium phosphate and ammonium chloride.
  • the mineral acids or their salts can optionally be adsorbed on to a substrate, such as, silica gel, or alumina.
  • a substrate such as, silica gel, or alumina.
  • Suitable organic acids include: carboxylic acids, such as, acetic acid, oxalic acid, glycolic acid, citric acid, tartaric acid, maleic acid and oxydisuccinic acid; halogenated carboxylic acids, such as, trifluoroacetic acid, heptafluorobutyric acid, dichloroacetic acid, and trichloroacetic acid; and sulfonic and sulfinic acids and their salts such as, p- toluenesulfonic acid, p-toluenesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 4-bromobenzene sulfonic acid, naphthalene sulfonic acid, (+)-10-camphor sulfonates, and alkyl benzene sulfonic acid.
  • carboxylic acids such as, acetic acid, oxalic acid, glycolic acid, citric acid,
  • Suitable pyridinium salts include, but are not limited to, pyridinium p- toluenesulfonate (PPTS), pyridinium p-toluenesulfinate, pyridinium hydrochloride, pyridinium hydrobromide, pyridinium hydrogen bisulfate, pyridinium hydrogen sulfate and mixtures thereof.
  • PPTS pyridinium p- toluenesulfonate
  • pyridinium hydrochloride pyridinium hydrobromide
  • pyridinium hydrogen bisulfate pyridinium hydrogen sulfate and mixtures thereof.
  • Suitable transition metal include, but are not limited to, molybedenyl(VI) acetylacetone; transition metal salts, such as lanthum trichloride, eerie ammonium nitrate; 2,3-dichloro-5,6,dicyano-p-benzoquinone, mercury(II) acetate, mercury(II) trifluroacetate, copper(II) acetylacetonate and tetracarbonylbis(cyclopentadienyl)diiron.
  • transition metal salts such as lanthum trichloride, eerie ammonium nitrate; 2,3-dichloro-5,6,dicyano-p-benzoquinone, mercury(II) acetate, mercury(II) trifluroacetate, copper(II) acetylacetonate and tetracarbonylbis(cyclopentadienyl)diiron.
  • Suitable polymers include, but are not limited to, polymeric ion exchange resins, or polyvinyl pyridines.
  • Suitable polymeric ion exchange resins include those of the Amberylst series, such as AMBERYLST®15, available from Rohm & Haas, the DOWEX® series, such as, DOWEX 50X8-50 available from Dow; REILLEX 424, available from Reilly Industries; the Amberlite series, such as AMBERLITE IRA-400, or AMBERLITE IR-1 18, available from Rohm & Haas; available from United Catalyst ; the ENVIROCAT series, such as ENNIROCAT EPZG, available from Contract Chemicals; and combinations thereof.
  • Suitable polyvinyl pyridines can be unsubstituted or substituted, such as substituted on the vinyl group and/or on the pyridine ring.
  • suitable polyvinyl pyridines include, but are not limited to, poly(4-vinylpyridine trifluoromethanesulfonate), poly(2-vinylpyridine trifluoromethanesulfonate), poly(4- vinylpyridine p-toluenesulfonate), poly(2-vinylpyridine p-toluenesulfonate), poly(4- vinylpyridine chloride), poly(2-vinylpyridine chloride), poly(4-vinylpyridine bromide), poly(2-vinylpyridine bromide), and mixtures thereof.
  • These polymeric catalysts have the additional advantage of being easy to separate from the surfactant produced.
  • Suitable catalysts include, bis(trimethysilyl)sulfate, iodotrimethylsilane, allytrimethyl silane, hexamethyldisilane, iodine, bromine, iron(II) sulfate, triphenylphosphine, aluminium sulfate, alkylether sulfuric acids, alkyl sulfuric acids, lithium perchlorate, lithium tetrafluoroborate, acetonyltriphenylphosphonium bromide, zirconium hydroxide, potassium cyanide, and platinum oxide.
  • Preferred catalysts include the sulfonic acids, Lewis acids, polyvinyl pyridines, methanesulfonic acid, AMBERYLST®15, acidic versions of DOWEX® and pyridinium p-toluenesulfonate (PPTS) with polyvinyl pyridines, pyridinium p-toluenesulfonate
  • PPTS p-toluenesulfonic acid
  • DOWEX® DOWEX®
  • AMBERYLST®15 methanesulfonic acid
  • the catalysts are preferably employed at amounts of about 0.1 mol % to about 20.0 mol %, more preferably from about 0.1 mol % to about 10.0 mol %, even more preferably from about 0.1 mol % to about 5.0 mol %, even more preferably still from about 0.1 mol % to about 2.0 mol %, even more preferably still from about 0.2 mol % to about 1.0 mol %.
  • Other suitable catalysts can be found in US patent No. U.S. Patent 4,272,394, and in PCT publications, WO 94/22800, WO 93/04153, WO96/00253 and WO 98/17379 all of which are incorporated herein by reference.
  • the reaction is conducted in the presence of a solvent, or mixtures of solvents.
  • the solvent be a polar aprotic solvent.
  • Suitable solvents include, but are not limited to, hexane, benzene, toluene, xylene, mesitylene, dichloromethane, tetrahydrofuran, dioxane, chloroform, diethylether, methyl tert-butylether, acetone, acrylonitrile, or the like.
  • the reaction is preferably conducted at temperatures ranging from about - 20°C to about 300°C, and more preferably from about -10°C to about 250°C.
  • the reaction is preferably conducted at pressures ranging from about 0.5 atmospheres to about 100 atmospheres, and more preferably from about 0.8 atmospheres to about 10 atmospheres.
  • the step of reacting vinyl ether with alkoxylated alcohol is conducted in the absence of a solvent.
  • the process is performed as a batch process. That is, the reaction is let proceeded to completion, or near completion, and then final product is removed.
  • the process is performed as a continuous process. That is, the product of the process is continuously removed from the reaction vessel while staring material is added at a comparable rate.
  • the vinyl ether is reacted with the alkoxylated alcohol at a mole ratio of from about 5 to about 1 , more preferably from about 3 to about 1 , more preferably still from about 1.5: 1 to about 0.90: 1 mole %.
  • the process may be conducted in an inert gas. This may be done by sparging with any suitable inert gas, such as nitrogen, helium, neon, or argon.
  • reaction step (c) may be followed by optional step (d).
  • Step (d) is a step in which the reaction step (c) is quenched, preferably by the addition of base.
  • the amount of the ether capped poly(oxyalkylated) alcohol surfactant present in the reaction mixture will depend upon many factors, including but not limited to, starting materials, temperature, catalyst selection and the like. Quenching stops the reaction, of the starting materials, and ensures that any ether capped poly(oxyalkylated) alcohol surfactant produced does not undergo further reaction or revert back to the starting materials.
  • step (c) produces a mixture which contains ether capped poly(oxyalkylated) alcohol surfactant, as well as, unreacted starting materials, catalyst and the products of any side reactions.
  • the quenching of the reaction of step (c) is done when the reaction mixture preferably contains at least 90%, more preferably 95% by weight of ether capped poly(oxyalkylated) alcohol surfactant.
  • the remaining 10%, more preferably 5% by weight comprises, unreacted starting material as well as products of side reactions, such as byproduct acetals.
  • the base may be optionally selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates alkali metal hydroxides, alkali metal alcoholates, alkanolamines, alkylamines, aromatic amines and mixtures thereof.
  • the base may be optionally selected from the group consisting of potassium carbonate, sodium carbonate, sodium bicarbonate sodium methoxylate, sodium ethoxylate, potassium tert-butyloxylate, triethylamine, triethanolamine and mixtures thereof.
  • the base may be in the form of an aqueous solution.
  • the aqueous solution may be at a temperature of from about 20°C to about 60°C.
  • step (c) is meant to include not only the ether-capped poly(oxyalkylated) alcohol surfactant but also any unreacted starting materials or any materials produced from side reactions, such as dimers, which would be present at the conclusion of step (c).
  • the process of the present invention may optionally further comprise a step (e).
  • Step (e) is removal of color bodies and/or odors from the product of steps (c), or (d).
  • removal of the color bodies and/or odors is obtained by contacting the product of steps (c) or (d) with a reagent.
  • the reagent can either be an oxidant, or a reductant.
  • Suitable oxidants include hydrogen peroxide.
  • Suitable reductants include sodium borohydride, and hydrogen over a palladium/carbon catalyst.
  • the color bodies and/or odors are removed by contacting the product of steps (c) or (d) first with an oxidant and then a reductant or first with a reductant and then an oxidant.
  • the ether-capped poly(oxyalkylated) alcohol surfactant produced in step (c) may optionally removed from the product of step (c) by centrifuging.
  • the ether-capped poly(oxyalkylated) alcohol surfactant product is then collect by means common in the art such as extraction. If desired, the surfactant may be further treated by stripping, distillation or various other means before use.
  • the surfactants made by the process disclosed herein may contain related impurities which will not adversely affect performance.
  • Neodol 1-7 (20.00 g, 41.6 mmol) is placed into a 500 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After releasing the vacuum with argon, sodium metal (0.05 g, 2.1 mmol) is added and the mixture stirred for 1 h at 120°C. After increasing the reaction temperature to 140°C, 1 ,2-epoxybutane (6.00 g, 83.2 mmol) is added dropwise over 30 minutes. After the addition is complete the mixture is stirred for an additional 1 h at 140°C. The solution is cooled to 90°C and neutralized with concentrated HCl.
  • Examples 2(a) to (i) are illustrative of some of the possible catalysts, work up options and relative amounts the starting materials that can be used in the present invention.
  • Neodol 91-8 (20.00 g, 39.1 mmol) is placed into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75 °C. After cooling to ambient and releasing the vacuum with argon, methylene chloride (100 ml) and cyclohexyl vinyl ether (5.43 g, 43.01 mmol) are added. The mixture is cooled to 0°C and pyridinium p-toluenesulfonate (0.43 g, 1.6 mmol) is introduced into the flask.
  • Neodol 91-8 (20.00 g, 39.1 mmol) and poly(4-vinylpyridinium p-toluenesulfonate) (0.43 g) are introduced into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at
  • Neodol 91-8 (20.00 g, 39.1 mmol) and poly(4-vinylpyridinium p-toluenesulfonate) (0.43 g) are introduced into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, cyclohexyl vinyl ether (4.94 g, 39.1 mmol) is added. The mixture is heated to 70-95°C overnight. The product mixture is separated from the catalyst by centrifugation to yield a liquid.
  • Neodol 91 -8 (20.00 g, 39.1 mmol) and poly(4-vinylpyridinium p-toluenesulfonate) (0.43 g) are introduced into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, cyclohexyl vinyl ether (4.94 g, 39.1 mmol) is added. The mixture is heated to 70-95°C overnight. The product mixture is washed with 20% potassium carbonate solution, dried and filtered to yield a liquid.
  • Neodol 91-8 (20.00 g, 39.1 mmol) and poly(4-vinylpyridinium p-toluenesulfonate) (7.82 g) are introduced into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, acetone (150 mL) and cyclohexyl vinyl ether (4.94 g, 39.1 mmol) are added. The mixture is stirred for three days, filtered and concentrated by rotary evaporation to yield a liquid.
  • Neodol 91-8 (20.00 g, 39.1 mmol) is placed into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, methylene chloride (100 ml) and cyclohexyl vinyl ether (4.84 g, 38.4 mmol) are added. The mixture is cooled to 0°C and pyridinium p-toluenesulfonate (0.39 g, 1.5 mmol) is introduced into the flask.
  • Neodol 91-8 (20.00 g, 39.1 mmol) is placed into a 250 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient, cyclohexyl vinyl ether (5.04 g, 39.9 mmol) is added. /?-Toluenesulfonic acid monohydrate (0.112 g, 0.59 mmol) is added to the mixture and stirred to dissolve. An exotherm is observed starting from 22°C and ending at 30°C, with the development of a precipitate. After 16 minutes of reaction time, the reaction pH is adjusted to >7 with triethanolamine, filtered and then stripped in a Kugelrohr oven (50°C, 0.1 mm Hg) to yield a quantitative amount of a near colorless liquid.
  • Neodol 91-8 (900.0 g, 1.76 mol) is placed into a 3 L three-necked rounded bottomed flask, fitted with a heating mantel, mechanical stirrer, internal thermometer, and vacuum argon take-off adapter. The contents are dried under vacuum at 80 °C for 30 min. A portion of the dry Neodol 91-8 (20 g) is set aside after the contents are cooled to room temperature. Cyclohexylvinyl ether (217.82 g, 1.73 mol) is then added to the reaction mixture.
  • the reagents are cooled to about 10 °C at which point methanesulfonic acid (1.80 mL) and the 20 g portion of Neodol set aside are combined and added to the reaction mixture via syringe, subsurface, in one portion.
  • the reaction mixture exotherms, ice bath controlled, to 22 °C.
  • the mixture is quenched with 15% sodium carbonate solution (35 mL).
  • the mixture is placed under vacuum by stripping in a Kugelrohr oven (25 °C, 0.1 mm Hg) for 10 min.
  • the product is filtered to yield a quantitative amount of a near colorless liquid.
  • Example 2(i) The procedure of Example 2(i) is repeated with the substitution of Neodol 91-8 for
  • Example 3 The procedure of Example 3 is repeated with the substitution of benzyl vinyl ether for cyclohexyl vinyl ether.
  • Example 2(i) The procedure of Example 2(i) is repeated with the substitution of 2-ethylhexyl vinyl ether for cyclohexyl vinyl ether and Tergitol- 15-S- 12 for Neodol 1-7.
  • Example 1 The procedure of Example 1 is repeated with the substitution of propylene oxide for 1 ,2- epoxybutane, cyclohexyl vinyl ether for 2-ethylhexyl vinyl ether, and Tergitol 15-S-9 for Neodol 1-7.
  • Example 8 The procedure of Example 1 is repeated with the substitution of cyclohexyl vinyl ether for 2-ethylhexyl vinyl ether and Neodol 25-9 for Neodol 1-7.
  • Example 8 The procedure of Example 1 is repeated with the substitution of cyclohexyl vinyl ether for 2-ethylhexyl vinyl ether and Neodol 25-9 for Neodol 1-7.
  • Neodol 1-7 Preparation of CnH 23 EO 7 -cyclohexyl acetal Neodol 1-7 (50.00 g, 104.0 mmol) is placed into a 1000 ml three-necked round-bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, methylene chloride (500 ml) and cyclohexyl vinyl ether (6.55g, 51.9 mmol) are added.
  • methylene chloride 500 ml
  • cyclohexyl vinyl ether 6.55g, 51.9 mmol
  • Tergitol 15-S-15 (100.0 g, 193.8 mmol) is placed into a 250 ml three-necked round- bottomed flask, fitted with a heating mantel, magnetic stirrer, internal thermometer, and vacuum/argon take-off adapter. The contents are dried under vacuum at 80 °C for 10 min. A portion of the dry Tergitol 15-S-15 (2 g) is set aside after the contents are cooled to room temperature. Cyclohexyl vinyl ether (24.21 g, 191.9 mmol) is then added to the reaction mixture.
  • the reagents are cooled to about 15 °C at which point methanesulfonic acid (0.28 g, 2.9 mmol) and the 2 g portion of Tergitol 15-S-15 set aside are combined and added to the reaction mixture via syringe, subsurface and in one portion.
  • the reaction mixture exotherms to 40 °C.
  • the reaction pH is adjusted to >7 with 15% sodium carbonate.
  • the mixture is placed under vacuum by stripping in a Kugelrohr oven (50 °C, 0.1 mm Hg) for 10 min.
  • the product is filtered to yield a quantitative amount of a near colorless liquid.
  • the following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope.
  • the ether-capped poly(oxyalkylated) alcohol surfactant produced by the process of the present invention may be used in other applications, such as a wetting agents, antifoaming agents, drilling muds, etc., in a wide range of fields, such as in biocides, pharmaceuticals, etc. Further examples of possible application for these surfactants can be found in "Nonionic Surfactants” edited by Martin J. Schinck, Surfactant Science Series, Mancel Dekker, NY, Volume 1; "Nonionic Surfactants: Physical Chemistry” edited by Martin J. Schinck, Surfactant Science Series, Mancel Dekker, NY, Volume 23; "Nonionic Surfactants: Polyoxyalkylen Block Copolymers” edited by Vaughn M.
  • CxyEzS Sodium C ⁇ x -C ⁇ v branched alkyl sulfate condensed with z moles of ethylene oxide CxyFA C 1 X -C 1 v fatty acid CxyEz A C ⁇ x _iy branched primary alcohol condensed with an average of z moles of ethylene oxide C24 N-Me Glucamide C12-C14 N-methyl glucamide
  • Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo holino-1.3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate.
  • Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
  • TPK Fatty Acid
  • Rapeseed fatty acid Borax Na tetraborate decahydrate
  • PAA Polyacrylic Acid ( w 4500)
  • Nai2(A102Si ⁇ 2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
  • NaSKS-6 Crystalline layered silicate of formula ⁇ -Na2Si2 ⁇ 5 Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
  • Nonaqueous Liquid Laundry Detergent compositions Non-limiting examples of bleach-containing nonaqueous liquid laundry detergent are prepared as follows.
  • LAS Powder for Use as a Structurant
  • NaLAS Sodium C12 linear alkyl benzene sulfonate
  • NaLAS powder is produced by taking a slurry of NaLAS in water (approximately 40-50% active) combined with dissolved sodium sulfate (3-15%) and hydrotrope, sodium sulfosuccinate (1-3%). The hydrotrope and sulfate are used to improve the characteristics of the dry powder.
  • a drum dryer is used to dry the slurry into a flake. When the NaLAS is dried with the sodium sulfate, two distinct phases are created within the flake. The insoluble phase creates a network structure of aggregate small particles (0.4-2 um) which allows the finished non-aqueous detergent product to stably suspend solids.
  • the NaLAS powder prepared according to this example has the following makeup shown in Table I.
  • Non-aqueous based heavy duty liquid laundry detergent compositions which comprise the capped nonionic surfactants of the present invention are presented below.
  • compositions are stable, anhydrous heavy-duty liquid laundry detergents which provide excellent rates of mixing with water as well as good stain and soil removal performance when used in normal fabric laundering operations.
  • Nonionic from example 8 5.0 1 - 20 MBAE Si5 2.0 0.5-10
  • Nonionic from example 6 0 3 0 0 0 0
  • Dimethicone is a 40(gum)/60(fluid) weight ratio blend of SE-76 dimethicone gum available from General Electric Silicones Division and a dimethicone fluid having a viscosity of 350 centistokes.
  • laundry detergent compositions are prepared in accord with the invention:
  • laundry detergent compositions are prepared in accord with the invention:
  • laundry detergent compositions are prepared in accord with the invention:
  • compositions were used neat to clean marble and dilute to clean lacquered wooden floors. Excellent cleaning and surface safety performance was observed.
  • Nonionic from example 8 3.0 - 1.0 - 3.2 - - -
  • Nonionic Surfactant 1 3.0 3.0
  • Amylase (0.8% active) 0.5 0.5
  • Te ⁇ olymer selected from either 60% acrylic acid/20% maleic acid/20% ethyl acrylate, or 70% acrylic acid/10% maleic acid/20% ethyl acrylate.
  • Pentaamineacetatocobalt(III) nitrate prepared as described hereinbefore; may be replaced by MnTacN.
  • compositions are suitable for use in the methods of the present invenetion. All percentages noted are by weight of the finished compositions, other than the perborate (monohydrate) component, which is listed as AvO.
  • EXAMPLES 42-43 Ingredients: Weight %
  • Pentaamineacetatocobalt(III) nitrate may be replaced by MnTacN.
  • Polyacrylate or Acusol 480N or polyacrylate/polymethacrylate copolymers are polyacrylate or Acusol 480N or polyacrylate/polymethacrylate copolymers.
  • the catalyst and enzymes are introduced into the compositions as 200-2400 micron composite particles that are prepared by spray coating, fluidized bed granulation, marumarizing, prilling, or flaking/grinding operations.
  • the protease and amylase enzymes may be separately formed into their respective catalyst/enzyme composite particles, for reasons of stability, and these separate compositions added to the compositions.
  • Nonionic Surfactant 2 2.0 3.0
  • Nonionic Surfactant 3 8.0 8.0
  • Nonionic surfactant according to Example 5 The following examples further illustrate ADD tablet compositions suitable for use in the methods of this present invention.
  • Nonionic Surfactant 3 3.0 3.0

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EP00984081A 1999-12-08 2000-12-08 Verfahren zur herstellung von etherverschlossenen poly(oxyalkylierten) alkoholtensiden Withdrawn EP1235778A2 (de)

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DE2302876A1 (de) * 1973-01-20 1974-08-01 Basf Ag Alkalistabile, oberflaechenaktive, schaumdaempfende mittel
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