WO2000014194A1 - Formulation nettoyante stable contenant un oxyde d'amine et un agent de blanchiment - Google Patents

Formulation nettoyante stable contenant un oxyde d'amine et un agent de blanchiment Download PDF

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Publication number
WO2000014194A1
WO2000014194A1 PCT/US1999/020846 US9920846W WO0014194A1 WO 2000014194 A1 WO2000014194 A1 WO 2000014194A1 US 9920846 W US9920846 W US 9920846W WO 0014194 A1 WO0014194 A1 WO 0014194A1
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WO
WIPO (PCT)
Prior art keywords
tertiary amine
amine oxide
formulation
bleaching agent
oxide
Prior art date
Application number
PCT/US1999/020846
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English (en)
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WO2000014194A9 (fr
Inventor
Suae-Chen Chang
Douglas H. Krzystowczyk
Dustin H. Thomas
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Albemarle Corporation
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Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Publication of WO2000014194A1 publication Critical patent/WO2000014194A1/fr
Publication of WO2000014194A9 publication Critical patent/WO2000014194A9/fr

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • This invention concerns stable cleaning formulations which contain both tertiary amine oxide product and a bleaching agent, e.g. NaOCl.
  • Tertiary amine oxides have long been recognized as efficacious surfactants in cleaning formulations.
  • Aqueous solutions of tertiary amine oxides have been found to be particularly suitable for use in making liquid cleaning formulations.
  • Commercially available aqueous tertiary amine oxide solutions are typically approximately 30 wt% solutions.
  • Tertiary amine oxides used in preparing commercial cleaning formulations are always accompanied by impurities, the qualitative identities and quantitative values of which are usually process dependent.
  • most tertiary amine oxides have amine, nitrosoamine and hydrogen peroxide impurities.
  • Metal impurities are also common.
  • the amine impurity typically corresponds to the tertiary amine from which the tertiary amine oxide was prepared, and the amine impurity can be present in an amount of up to about 2 wt%, based on the total weight of tertiary amine oxide, impurities, and water.
  • the tertiary amine oxide concentration amounts to at least 28 wt%, on the same basis.
  • tertiary amine oxide product or tertiary amine oxide products to differentiate the combination(s) from the tertiary amine oxide molecule.
  • bleaching agents in the cleaning formulations is recognized to enhance the formulation's disinfectant qualities. Combining tertiary amine oxide products with the bleaching agents improves the cleaning performance and the viscosity of the formulation.
  • This invention makes possible the provision of a cleaning formulation which contains tertiary amine oxide product and a bleaching agent in which the bleaching agent is relatively stable and/ or is not so readily depleted as in prior art formulations.
  • this invention provides a process by which such cleaning formulations can be formed.
  • This invention relates to a cleaning formulation which comprises a bleaching agent and tertiary amine oxide product, the bleaching agent and tertiary amine oxide product being in a weight ratio of from 1:3 to 30: 1.
  • the tertiary amine oxide product used contains (i) from 28.5 to 32 wt% tertiary amine oxide, (ii) amine impurity, and (iii) hydrogen peroxide in an amount of no more than 0.6 wt%, with the proviso that the amount of hydrogen peroxide that is present is sufficient to reduce the level of amine impurity and thereby increase storage stability of the formulation.
  • the formulation is provided with a pH within the range of from 11 to 13.5.
  • the cleaning formulations of this invention can sustain less than about a 20% loss of the activity of the bleaching agent in the formulation over a 6-month period when maintained at a temperature within the range of from 15 to 25 °C. Most preferably they undergo no more than 5 to 15% loss over a 6-month period at a temperature within the just-recited range.
  • this invention relates to a process for preparing a stable cleaning formulation, which process comprises: a) forming at least a portion of the formulation from a bleaching agent and a tertiary amine oxide product in a weight ratio of the former to the latter of from 1:3 to 30: 1, wherein the tertiary amine oxide product used contains (i) from 28.5 to 32 wt% tertiary amine oxide, (ii) amine impurity, and (iii) hydrogen peroxide in an amount of no more than 0.6 wt%, with the proviso that the amount of hydrogen peroxide that is present is sufficient to reduce the level of amine impurity and thereby increase storage stability of the formulation; and b) providing the formulation with a pH of at least about 11.
  • Still another embodiment of this invention is a method of increasing the effective life of an aqueous bleaching solution, which method comprises having in the formulation hydrogen peroxide in an amount of sufficient to reduce the level of amine impurity without depleting the amount of bleaching agent present.
  • the tertiary amine oxide product can be conventionally produced by the oxidation of a tertiary amine with hydrogen peroxide. See, for example, U.S. 4,247,480, U.S. 4,960,934, U.S. 4,970.340, U.S. 5,055,232, U.S. 5,055,614, U.S. 5,120,469, U.S. 5,164,120, U.S.
  • R 1 R 2 R 3 N wherein R, and R 2 are, independently, methyl or ethyl groups and R 3 is an aliphatic, monovalent hydrocarbon group containing in the range of 10 to 14 carbon atoms. C 12 and C, 4 straight chain alkyl groups are preferred. Preferred are dodecyldimethylamine and tetradecyldimethylamine. Most highly preferred is tetradecyldimethylamine. Between the dodecyl and tetradecyl species, the latter are preferred.
  • the tertiary amine oxide which constitutes the major component of the tertiary amine oxide product, can be represented by the formula:
  • Suitable tertiary amine oxides include decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, tetradecyldiethylamine oxide, dodecylethylmethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, dodecyldiethylamine oxide, tetradecylethylmethylamine oxide, lauryldimethylamine oxide, myristyldimethylamine oxide, lauryldiethylamine oxide, laurylethylmethylamine oxide, myristylethylmethylamine oxide, myristyldiethylamine oxide, and the like.
  • Amine oxide products containing mixtures of two or more such amine oxides are also suitable.
  • the dodecyl and tetradecyl species are preferred because of their greater effectiveness in the practice of this invention.
  • dodecyldimethylamine oxide is preferred.
  • tetradecyldimethylamine oxide is the most highly preferred component as formulations of this invention based thereon have shown the greatest superiority in bleach stability performance.
  • the tertiary amine and hydrogen peroxide impurities and their amounts in the tertiary amine oxide product are process dependent.
  • impurities which include, one or more of, iron chlorides, nickel chlorides, alkali metal chlorides, especially sodium chloride and magnesium, calcium, titanium, cobalt and copper compounds.
  • iron chlorides, nickel chlorides, alkali metal chlorides, especially sodium chloride and magnesium, calcium, titanium, cobalt and copper compounds The adverse affect on bleaching agent destabilization/depletion can be significant if these other impurities are present in large amounts, which they seldom are.
  • the nickel, iron and alkali metal chlorides are discussed further, infra.
  • the tertiary amine oxide product contain a low level of amine impurity. It is preferred that the amine impurity constitute less than about
  • tertiary amine oxide product 0.6 wt% of the tertiary amine oxide product. More preferred tertiary amine oxide products are those which have about 0.2 wt% amine impurity.
  • the hydrogen peroxide impurity concentration in the tertiary amine oxide product used in preparing the formulation is, in most cases, kept low, say no more than about 0.6 wt%. Hydrogen peroxide reacts with the bleaching agent to deplete it. However, if all other destabilizing and depleting factors are low, it may be permissible and even desirable to have from 0.15 to 1.0 wt% hydrogen peroxide in the tertiary amine oxide product. The desirability arises from the fact that hydrogen peroxide can be beneficial to the color and viscosity qualities of the tertiary amine oxide product used in making the formulation.
  • the tertiary amine oxide product contain from 0.2 to 0.8 wt% hydrogen peroxide.
  • the foregoing weight percents are based on the total weight of the tertiary amine oxide product.
  • the hydrogen peroxide concentration in the cleaning formulation can be adjusted downwardly by employing an enzyme, such as catalase, in the formulation.
  • Catalase catalyzes the decomposition of hydrogen peroxide to oxygen and water.
  • Catalase II which is an enzyme derived from Corynebact Glutamicum is preferred over Catalase I, which is derived from cow liver.
  • Catalase I is usually used in an amount of from 50 to 750 ppm depending on the amount of hydrogen peroxide initially present. Catalase II is used in lesser amounts, say 10 to 50 ppm, for a like amount of hydrogen peroxide.
  • the ppm basis is by weight of the tertiary amine oxide product.
  • the tertiary amine oxide products used in this invention contain no detectable quantity, or at most relatively low amounts, of dissolved Ni or nickel-containing compounds such as NiCl 2 , and/or dissolved Fe or iron-containing compounds such as FeCl 3 .
  • Tertiary amine oxide products having from 0 to 1 ppm Ni can be used.
  • the Ni content, if any, is preferably less than about 0.5 ppm and most preferably below 0.4 ppm (wt/wt).
  • the Fe content, if any, is preferably below 1.0 ppm, and most preferably below 0.5 ppm.
  • Ni contents of up to 3 ppm and Fe contents of up to 20 ppm are tolerable. These ppm values are based on the weight of the total formulated product, . e. , tertiary amine oxide product plus bleach plus impurities.
  • the tertiary amine oxide is an antagonist towards the bleaching agent in the cleaning formulation and its use must be moderated. It has been found that a good balance between surfactant function and destabilization/depletion of the bleaching agent is achieved when the weight ratio of the bleaching agent to tertiary amine oxide product is within the range of from 0.33:1 to 30: 1, and preferably within the range of from 0.4: 1 to 10: 1. For dodecyldimethylamine oxide and tetradecyldimethylamine oxide, the weight ratio is preferably within the range of from 0.5: 1 to 5: 1.
  • Tertiary amine oxide products useful in this invention can be conveniently produced in accordance with U.S. 4,247,480 or a modification thereof.
  • the modified process entails running the process of U.S. 4,247,480 until the reaction mass contains from 1 to 2.5% of the original amount of tertiary amine reactant fed. Also, at this time, there will be present unreacted hydrogen peroxide and carbon dioxide.
  • the reaction mass temperature is then about 55 °C.
  • the reaction mass is then removed from the reactor and allowed to cool to a temperature of from 10 to 35°C. This cooling can occur in a separate process vessel or can occur in drums in which the product will be shipped. If the cooling occurs in the latter, then the drums should be vented to allow for the escape of off-gases.
  • tertiary amine oxide products used in this invention may also be purchased under the
  • ADMOX-12 amine oxide contains from 28.5 to 32 wt% dodecyldimethylamine oxide, no more than 0.5 wt% dodecyldimethylamine, no more than 0.3 wt% hydrogen peroxide, and from 0 to 1 ppm Ni.
  • ADMOX- 14 amine oxide contains from 29 to 31 wt% tetradecyldimethylamine oxide, no more than 0.5 wt% tetradecyldimethylamine, no more than 0.5 wt% hydrogen peroxide, and from 0 to 1 ppm Ni.
  • ppm is on a weight basis.
  • the tertiary amine oxide products useful in the cleaning formulations of this invention will have a pH of from 7 to 8 prior to being used in the formulations.
  • the content of tertiary amine oxide in the cleaning formulations of this invention is typically from 0.2 to 5 wt%.
  • the cleaning formulations of this invention can also contain constituents other than those described above.
  • the formulations can contain emulsifiers, chelating agents, fragrances, detergents, buffers, viscosifiers, surfactants, abrasives, solvents, and like ingredients.
  • Such other constituents should, of course, be devoid of quantities of amine that would destabilize or deplete the bleach content of the formulation in which the constituents are being used.
  • the pH of the cleaning formulation can be adjusted by the use of a base such as NaOH, Mg(OH) 2 , or Ca(OH) 2 so as to obtain the before-mentioned requisite value of at least about 11, and preferably in the range of from 12 to 13.5, and most preferably within the range of from 12.2 to 13.
  • the pH of the cleaning formulation is determined by use of an ORION model 290A pH meter.
  • a dodecyldialkylamine oxide based product e.g. , ADMOX-12 amine oxide
  • a tetradecyldialkylamine oxide product e.g. , ADMOX- 14 amine oxide
  • the pH of such products before use in producing the aqueous bleach formulation be within the range of from 7 to 8.
  • the temperature of the cleaning formulation will have a bearing on the stability/depletion of the bleaching agent. It has been found that it is very beneficialent to maintain the cleaning formulation most of the time at a temperature less than 40°C and preferably between 10 and
  • the bleaching agents used in the cleaning formulations of this invention are generally provided as aqueous solutions in which the bleaching agent comprises from 1 to 8 wt% and preferably from 1 to 2.5 wt%, the weight percentages being based on the total weight of the solution.
  • bleaching agents are hypohalites (e.g. , sodium hypochlorite (NaOCl), potassium hypochlorite, or sodium hypobromite), haloamines, haloimines, haloamides, haloimides, and the like. Due to its ready availability, NaOCl in a 5 to 5.5 wt% aqueous solution is preferred.
  • EXAMPLES The following Examples, wherein all percentages are on an active basis and are based on the total weight of each sample, illustrate the destabilizing/depletion effect that different tertiary amine oxide products have, according to their tertiary amine reactant content, on bleaching agents.
  • a first set of samples was prepared having a pH of 13. These were comprised of 1 wt% sodium hydroxide (for pH adjustment), 2 wt% sodium hypochlorite, 1 wt% tertiary amine oxide product and 96 wt% water.
  • a second set of samples was prepared having a pH of 12 and these samples were comprised of 0.046 wt% sodium hydroxide, 2 wt% sodium hypochlorite, 1 wt% tertiary amine oxide product and 97.954 wt% water.
  • a third set of samples was prepared having a pH of 11. In this case these samples were comprised of 2 wt% sodium hypochlorite,
  • ADMOX-12 amine oxide (Albemarle Corporation), (Specification: 31.7 wt% dodecyl dimethyl tertiary amine oxide);
  • ADMOX-14 amine oxide (Specification: 30.3 wt% tetradecyl dimethyl tertiary amine oxide); ⁇ BARLOX-12 amine oxide (Lonza Inc.) (Specification: 29.6 wt% lauryl dimethyl tertiary amine oxide);
  • AMMONYX LO (Stephan Co.) (Specification: 30.6 wt% lauryl dimethyl tertiary amine oxide);
  • AMMONYX MO (Specification: 30.1 wt% myristyl dimethyl tertiary amine oxide);
  • the sodium hydroxide used to prepare the samples was from J.T. Baker, 50 wt% aqueous.
  • the sodium hypochlorite was Clorox brand, typically 5.25 wt% active ingredient and was measured each time before use.
  • the water used was distilled and deionized water.
  • hypochlorite concentration was periodically determined on the following schedule:
  • hypochlorite is ⁇ 1 wt% of sample.
  • the wt% of the NaOCl of the samples was determined by iodometry using the following procedure: As per the schedule, a 3 to 4 gram sample was weighed into a 250-mL Erlenmeyer flask. To the flask was then added 50 mL of a 55 potassium iodide solution, followed by 25 mL of glacial acetic acid. The resultant solution was then titrated to a brown color with a 0.1 N sodium thiosulfate solution. Then, 5 drops of starch indicator were added and then titration was continued until a colorless endpoint was obtained. The following formula was then used to calculate the wt% of hypochlorite present at the selected time interval:
  • wt% sodium hypochlorite mLs of sodium thiosulfate used x 0.1 x 0.03772 x 100 grams of sample used
  • water-soluble means that the material in question has sufficient solubility in water at ambient room temperature to form a solution having a concentration of the material specified herein. Preferably the material will dissolve in still higher amounts in water, but this is not a requirement.
  • chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g. , another component, or solvent). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or formulation as such changes, transformations and/or reactions (e.g.

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Abstract

L'invention concerne la découverte des facteurs provoquant une déstabilisation et un appauvrissement de l'agent de blanchiment dans des formulations fabriquées à partir d'oxydes d'amine tertiaire. On a en effet découvert que pour surmonter ces problèmes, une quantité suffisante de peroxyde d'hydrogène doit être présente dans une formulation aqueuse renfermant un agent de blanchiment et un oxyde d'amine tertiaire, afin de pouvoir réduire la quantité d'impuretés aminées présente dans le produit d'oxyde d'amine utilisé pour former le mélange. La formulation susmentionnée doit par ailleurs renfermer une base hydrosoluble (par exemple NaOH) pour présenter un pH d'au moins 11, et de préférence entre 12 et 13,5.
PCT/US1999/020846 1998-09-10 1999-09-10 Formulation nettoyante stable contenant un oxyde d'amine et un agent de blanchiment WO2000014194A1 (fr)

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US15104298A 1998-09-10 1998-09-10
US09/151,042 1998-09-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2182695A1 (es) * 2001-05-03 2003-03-01 Rico Agustin Gomez Procedimiento de preparacion de un limpiador universal y producto resultante.
WO2022256690A1 (fr) * 2021-06-04 2022-12-08 W.M. Barr & Company, Inc. Composition de nettoyage et procédé d'élimination de taches de bardeaux de toiture

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206534A1 (fr) * 1985-05-30 1986-12-30 The Clorox Company Agent de nettoyage aqueux épaissi
US4839077A (en) * 1986-08-07 1989-06-13 The Clorox Company Thickened bleach composition
US4842757A (en) * 1988-01-21 1989-06-27 The Clorox Company Thickened liquid, improved stability abrasive cleanser
WO1994010272A1 (fr) * 1992-11-03 1994-05-11 The Procter & Gamble Company Nettoyage a l'aide d'agents tensio-actifs a courtes chaines
WO1995018209A1 (fr) * 1993-12-29 1995-07-06 Reckitt & Colman Inc. Compositions a base d'hypochlorite de metal alcalin epaissies
WO1998030672A1 (fr) * 1997-01-10 1998-07-16 Reckitt & Colman South Africa (Pty) Limited Compositions organiques ameliorees ou ameliorations relatives a ces compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206534A1 (fr) * 1985-05-30 1986-12-30 The Clorox Company Agent de nettoyage aqueux épaissi
US4839077A (en) * 1986-08-07 1989-06-13 The Clorox Company Thickened bleach composition
US4842757A (en) * 1988-01-21 1989-06-27 The Clorox Company Thickened liquid, improved stability abrasive cleanser
WO1994010272A1 (fr) * 1992-11-03 1994-05-11 The Procter & Gamble Company Nettoyage a l'aide d'agents tensio-actifs a courtes chaines
WO1995018209A1 (fr) * 1993-12-29 1995-07-06 Reckitt & Colman Inc. Compositions a base d'hypochlorite de metal alcalin epaissies
WO1998030672A1 (fr) * 1997-01-10 1998-07-16 Reckitt & Colman South Africa (Pty) Limited Compositions organiques ameliorees ou ameliorations relatives a ces compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2182695A1 (es) * 2001-05-03 2003-03-01 Rico Agustin Gomez Procedimiento de preparacion de un limpiador universal y producto resultante.
WO2022256690A1 (fr) * 2021-06-04 2022-12-08 W.M. Barr & Company, Inc. Composition de nettoyage et procédé d'élimination de taches de bardeaux de toiture

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