US3402128A - Novel composition and method - Google Patents

Novel composition and method Download PDF

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Publication number
US3402128A
US3402128A US420180A US42018064A US3402128A US 3402128 A US3402128 A US 3402128A US 420180 A US420180 A US 420180A US 42018064 A US42018064 A US 42018064A US 3402128 A US3402128 A US 3402128A
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US
United States
Prior art keywords
active
oxygen
percent
aminoxide
compounds
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.)
Expired - Lifetime
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US420180A
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English (en)
Inventor
Puchta Rolf
Fries Walter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of US3402128A publication Critical patent/US3402128A/en
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/037—Stabilisation by additives
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • This invention relates to liquid concentrates containing active oxygen and having surface-active properties. More specifically, this invention relates to aqueous concentrates of per-oxygen compounds, such as hydrogen peroxide and the like, and a surface-active aminoxide stabilizer.
  • the stabilizers are known and described in the prior art, such as magnesium salts, and especially magnesium silicates, in addition to alkali-pyrophosphates or alkali polyphosphates, alkali stannates, alkali silicates, and others are used for regulating the degree to which oxygen is liberated in diluted and ready-touse washing and States Patent bleaching fluids containing per-oxygen compounds.
  • the concentrate has a pH of from 1 to 10 and preferably has a pH within the range of from 3 to 9 to prevent fiber damage in washing and bleaching processes.
  • most of the known stabilizing agents with the exception of the abovenamed acids, acid salts, and a small number of organic compounds, are not suitable for manufacturing liquid concentrates containing oxygen, which are capable of long storage life.
  • the surface-active aminoxides of this invention are valuable tensides which have detergent or wetting properties which vary according to the nature and structure of the alkyl side-chains attached to the amine compound. These properties of high-molecular-weight aminoxide now make it possible to manufacture a combined detergentbleaching concentrate, in which the bleaching compound comprises active-oxygen-containing materials, such as compounds of hydrogen peroxide or adducts of hydrogen peroxide to urea, melamine, alkali borates, alkali ortho-phosphates, alkali polyphosphates, or the like.
  • the compositions of this invention are in marked contrast to prior art compositions which employ stabilizing agents that lack surface-active properties.
  • the surface-active properties of prior art compositions are obtained by the addition of tensides to the oxygen compound, which, as a rule, nullify or counteract the stabilizing agents and promote relatively rapid loss of active oxygen from the composition.
  • aminoxide nitrogen and ether oxygen are separated from one another by at least 3 carbon atoms and can be used as surface-active aminoxides having stabilizing properties.
  • Glycol or polyglycol ether groups may be located between the hydrophobic part of the molecule and the aminoxide radical.
  • the aminoxides of this invention comprise compounds of the general formula /R4 R1X(R --0)nR N 0 where R signifies a saturated higher alkyl radical with 6 to 20 carbon atoms, X a chalcogen such as oxygen, sulfur, selenium and telurium, oxygen or sulfur atom being preferred, R an ethylene, propylene or oxypropylene radical, n a whole number from to 18, perferably from 0 to 10, R a radical with at least 3 or 4 carbon atoms and containing, if desired, free hydroxy groups, and R and R signify lower saturated alkyl or alkylol radicals with at most 5, preferably with at most 3, carbon atoms.
  • R signifies a saturated higher alkyl radical with 6 to 20 carbon atoms
  • X a chalcogen such as oxygen, sulfur, selenium and telurium, oxygen or sulfur atom being preferred
  • R an ethylene, propylene or oxypropylene radical
  • n a whole number
  • the ether oxygen atom or thioether sulfur atom present in the surface-active aminoxides to be used according to the invention improves the solubility of the products, which is still further improved by any glycolether or polyglycolether radicals that may be present.
  • substantially more than 24 carbon atoms may be present in the aminoxides to be used according to this invention; the maximum of 24 carbon atoms mentioned refers to the hydrophobic part of the molecule which, in the aboverepresented formula, refers to the radical R
  • the advantages of these aminoxides are not limited merely to the better solubility of the compounds, but are also to be seen in a better stabilizing effect.
  • the upper limit of the hydrogen peroxide content of the concentrates lies preferably at 60 weight percent H 0
  • the surface-active aminoxides of this invention have especially pronounced stabilizing effects in an acid-toneutral milieu, i.e., at a pH from 1 to 7.
  • the aminoxide may be used in a strongly acid (pH of 2 to 4), or weakly acid (from 4 to 68) environment. Stabilization, however, may also be achieved from several days to several weeks in a weakly alkaline milieu, i.e., at a pH from 7.2 to 8.
  • the pH of the environment may be made more strongly alkaline.
  • a pH up to about is suitable for this purpose.
  • the shelf life of the concentrates decreases as the alkalinity increases, so that pH values over 10.5 do not give optimum results with respect to stability, however, concentrates having higher pH values may also be used.
  • compositions of this invention may be stored as concentrates in a weakly acid, or neutral, or weakly alkaline mixture, which are adjusted to the desired higher pH values by the addition of alkaline or acidic compounds upon being used.
  • Conventional alkaline reagents may be used for increasing the pH of the milieu.
  • Alkaline salts are especially useful, such as those commonly used as additives in bleaching and washing, for example, the alkaline or alkali carbonates, bicarbonates, ortho-phosphates, pyro-phosphates, and polyphosphates such as tripolyphosphates, borates, silicates, and the like, and various mixtures thereof.
  • the composition supplying the active oxygen comprises the perhydrates of the above-mentioned inorganic salts, the alkaline materials will generally be present in sufiicient quantities, so that addition of other alkaline compounds will not generally be necessary.
  • Acidic substances may also be added to the compositions of this invention in order to lower the pH value to 9 or less. If condensed phosphates are to be used, the weakly acid glassy phosphates of the Graham salt type have proven to be particularly well suited for this purpose.
  • Non-reducing inorganic or organic acids or acid salts are used for adjusting the pH values in the acid range, if necessary.
  • Phosphoric acid as well as the polyphosphoric acids are suitable in addition to sulfuric acid, citric acid, malonic acid, tartaric acid, ascorbic acid, and the like, or various mixtures thereof.
  • Some of these acids are already well known in the prior art as oxygen stabilizers and, in some cases, permit a reduction of the amount of aminoxides present in the composition of this invention, or their replacement by other tensides.
  • the amount of aminoxides serving as stabilizers in accord with this invention can vary within Wide limits. These compounds may be present in quantities amounting to 2 to 40 percent by weight, and preferably 5 to 25 percent by weight of the total composition. With reference to the hydrogen peroxide present in the free or bound state, the aminoxides are present in quantities of at least 10 percent by weight, however, may be used in amounts of up to 200 percent by weight, and preferably in amounts from 30 to 100 percent by weight.
  • the aminoxides of this invention may be used in combination with other substances in the preparation of compositions containing active oxygen.
  • These substances generally comprise tensides of the carboxylate, sulfate and sulfonate type having saturated molecular hydrophobic radicals attached thereto.
  • Non-ionogenic tensides are particularly suitable, especially those comprising the addition of ethylene oxide to either fatty acids or fatty alcohols in addition to the ethylene oxide addition products of saturated alkyl phenols, such as the nonyl phenols.
  • Pluronic compounds are generally high-molecular-weight polypropylene glycol ethers, which are rendered water-soluble by the addition of ethylene oxide to the molecular chain, whereas the tetronic types generally comprise addition products of propylene oxide and diamines such as ethylene diamine.
  • Other compounds suitable in this respect comprise alkali metal pyrophosphates or polyphosphates. These compounds may be used in the form of their acid salts or as acidified preparations.
  • hydrotropic substances may also be used in the compositions of this invention. Examples of suitable hydrotropic compounds comprise the alkali metal salts of toluenesulfonic acid or xylenesulfonic acid. Dirt holders, such as carboxymethylcelluloses or oxidation-resistant optical brighteners, can also be present.
  • liquid concentrates containing active oxygen shall be understood hereby to mean aqueous solutions with a content of at least 3 to weight percent, and pref: erably 10 to 70 weight percent and most preferably 10 to 40 weight percent, of H 0
  • the H 0 may also be preent, wholly or partially, in the form of addition products which it forms with urea, melamine, alkali borates, alkali ortho-phosphates or polyphosphates, or the like, which have been dissolved or suspended in water.
  • concentration of any undissolved hydrogen peroxide compounds that may be present in the liquid concentrates containing active oxygen ranges from 3 to 40 weight percent, and preferably from 10 to 25 weight percent.
  • the C -alkyl group being present in the aminoxide as used in the Examples I-IV was derived from coconut fatty acids.
  • a liquid storage-stable active-oxygen containing detergent bleaching concentrate consisting essentially of water, hydrogen peroxide in an amount of from 3 to 90 wt.-percent and a surface active aminoxide of the formula:
  • a liquid storage-stable, active-oxygen containing detergent-bleaching concentrate according to claim 10 consisting essentially of Wt.-percent H 0 5 Aminoxide 10 K P O 20 Toluene sulfonate 8 References Cited UNITED STATES PATENTS 3,194,768 7/1965 Lindner et al 252186 X 3,202,714 8/1965 Zimmerer et al. 252117 X 3,206,512 9/1965 Koebner et al. 252152 3,252,979 5/1965 Oswald et al. 260-584 FOREIGN PATENTS 626,979 6/ 1963 Belgium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
US420180A 1964-01-04 1964-12-21 Novel composition and method Expired - Lifetime US3402128A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEH0051286 1964-01-04
DEH52856A DE1299092B (de) 1964-01-04 1964-05-30 Fluessige, Aktivsauerstoff enthaltende Konzentrate mit grenzflaechenaktiven Eigenschaften

Publications (1)

Publication Number Publication Date
US3402128A true US3402128A (en) 1968-09-17

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US420180A Expired - Lifetime US3402128A (en) 1964-01-04 1964-12-21 Novel composition and method
US420181A Expired - Lifetime US3388069A (en) 1964-01-04 1964-12-21 Liquid active oxygen detergent bleaching concentrate

Family Applications After (1)

Application Number Title Priority Date Filing Date
US420181A Expired - Lifetime US3388069A (en) 1964-01-04 1964-12-21 Liquid active oxygen detergent bleaching concentrate

Country Status (9)

Country Link
US (2) US3402128A (OSRAM)
BE (1) BE657865A (OSRAM)
CH (1) CH467721A (OSRAM)
DE (2) DE1271885B (OSRAM)
DK (1) DK120958B (OSRAM)
ES (1) ES307775A1 (OSRAM)
FR (1) FR1419437A (OSRAM)
GB (2) GB1089997A (OSRAM)
NL (1) NL6414208A (OSRAM)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016243A (en) * 1976-06-10 1977-04-05 Ppg Industries, Inc. Hydrogen peroxide stabilization with 3-n-morpholinylpropionitriles
US4025609A (en) * 1975-05-19 1977-05-24 Kao Soap Co., Ltd. Process for preparing stable sodium percarbonate
US4035471A (en) * 1976-06-10 1977-07-12 Ppg Industries, Inc. Hydrogen peroxide stabilization with cyanoalkyl ethers of trialkanolamines
US4229313A (en) * 1977-09-02 1980-10-21 Imperial Chemical Industries Limited Alkali metal hypochlorite bleaching and cleaning compositions thickened with branch chain amine oxides
WO1981000106A1 (en) * 1979-06-27 1981-01-22 Sherex Chem Amine oxide foam stabilizers for alkyl benzene sulfonate foaming agents
US4490279A (en) * 1979-10-17 1984-12-25 Basf Wyandotte Corporation Foam-stabilized compositions
US4970341A (en) * 1987-02-24 1990-11-13 Ethyl Corporation Amine oxide process
US5102571A (en) * 1988-11-11 1992-04-07 Imperial Chemical Industries Plc Aqueous bleaching composition comprising sodium perborate tetrahydrate and aqueous detergent compositions containing the same
EP0779357A1 (en) * 1995-12-16 1997-06-18 The Procter & Gamble Company Stable emulsions comprising a hydrophobic liquid ingredient
EP1010749A3 (en) * 1995-03-27 2000-09-20 The Procter & Gamble Company Activated liquid bleaching compositions
US20060111261A1 (en) * 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE795085A (fr) * 1972-03-10 1973-05-29 Benckiser Knapsack Gmbh Procede de blanchiment de fibres cellulosiques seules ou en melange avec des fibres synthetiques
US3869401A (en) * 1972-12-04 1975-03-04 Du Pont Stabilized acidic hydrogen peroxide solutions
US5008036A (en) * 1975-08-18 1991-04-16 Laurel Industries, Inc. Colloidal sols of antimony pentoxide in an aqueous medium and their preparation
US4348301A (en) * 1975-08-18 1982-09-07 Ppg Industries, Inc. Process for making colloidal sols of antimony pentoxide in an aqueous medium
US4130501A (en) * 1976-09-20 1978-12-19 Fmc Corporation Stable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same
DE3364292D1 (en) * 1982-02-03 1986-08-07 Procter & Gamble Oxygen-bleach-containing liquid detergent compositions
GB8830296D0 (en) * 1988-12-28 1989-02-22 Unilever Plc Bleaching composition
DE3906044A1 (de) * 1989-02-27 1990-08-30 Henkel Kgaa Bleichendes fluessigwaschmittel
EP0662120A4 (en) * 1992-09-25 1998-04-29 Procter & Gamble DETERGENT CONTAINING NON-ALCOXYLATED NON-IONIC SURFACTANT.
NL1000065C2 (nl) * 1995-04-05 1996-10-08 Dija Zeist B V Werkwijze en middel voor het reinigen van oppervlakken.
FR2766724B1 (fr) * 1997-07-31 1999-10-22 Irdec Sa Compositions decontaminantes non agressives
CN117285141A (zh) * 2022-06-17 2023-12-26 中国石油化工股份有限公司 一种酸性含硫污水的除硫剂、其制备方法及除硫方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE626979A (OSRAM) * 1962-02-13 1963-05-02
US3194768A (en) * 1960-07-07 1965-07-13 Henkel & Cie Gmbh Production of storage stable active oxygen containing liquid concentrates
US3202714A (en) * 1961-12-04 1965-08-24 Procter & Gamble Oxy containing tertiary amine oxides
US3206512A (en) * 1962-02-07 1965-09-14 Marchon Products Ltd N-dialkyl-alkyl-and-alkaryl-oxyalkylamine oxides
US3252979A (en) * 1961-09-06 1966-05-24 Exxon Research Engineering Co Peroxide-containing adducts of amine compounds and the preparation thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2169976A (en) * 1934-01-26 1939-08-15 Ig Farbenindustrie Ag Process of producing assistants in the textile and related industries
NL250152A (OSRAM) * 1959-04-20
NL122204C (OSRAM) * 1959-08-08
DE1219614B (de) * 1960-07-14 1966-06-23 Henkel & Cie Gmbh Waschmittel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194768A (en) * 1960-07-07 1965-07-13 Henkel & Cie Gmbh Production of storage stable active oxygen containing liquid concentrates
US3252979A (en) * 1961-09-06 1966-05-24 Exxon Research Engineering Co Peroxide-containing adducts of amine compounds and the preparation thereof
US3202714A (en) * 1961-12-04 1965-08-24 Procter & Gamble Oxy containing tertiary amine oxides
US3206512A (en) * 1962-02-07 1965-09-14 Marchon Products Ltd N-dialkyl-alkyl-and-alkaryl-oxyalkylamine oxides
BE626979A (OSRAM) * 1962-02-13 1963-05-02

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025609A (en) * 1975-05-19 1977-05-24 Kao Soap Co., Ltd. Process for preparing stable sodium percarbonate
US4016243A (en) * 1976-06-10 1977-04-05 Ppg Industries, Inc. Hydrogen peroxide stabilization with 3-n-morpholinylpropionitriles
US4035471A (en) * 1976-06-10 1977-07-12 Ppg Industries, Inc. Hydrogen peroxide stabilization with cyanoalkyl ethers of trialkanolamines
US4229313A (en) * 1977-09-02 1980-10-21 Imperial Chemical Industries Limited Alkali metal hypochlorite bleaching and cleaning compositions thickened with branch chain amine oxides
WO1981000106A1 (en) * 1979-06-27 1981-01-22 Sherex Chem Amine oxide foam stabilizers for alkyl benzene sulfonate foaming agents
US4263177A (en) * 1979-06-27 1981-04-21 Sherex Chemical Company, Inc. Amine oxide foam stabilizers for alkyl benzene sulfonate foaming agents
US4490279A (en) * 1979-10-17 1984-12-25 Basf Wyandotte Corporation Foam-stabilized compositions
US4970341A (en) * 1987-02-24 1990-11-13 Ethyl Corporation Amine oxide process
US5102571A (en) * 1988-11-11 1992-04-07 Imperial Chemical Industries Plc Aqueous bleaching composition comprising sodium perborate tetrahydrate and aqueous detergent compositions containing the same
EP1010749A3 (en) * 1995-03-27 2000-09-20 The Procter & Gamble Company Activated liquid bleaching compositions
EP0779357A1 (en) * 1995-12-16 1997-06-18 The Procter & Gamble Company Stable emulsions comprising a hydrophobic liquid ingredient
EP0910465A4 (OSRAM) * 1995-12-16 1999-04-28
US20060111261A1 (en) * 2004-11-19 2006-05-25 The Procter & Gamble Company Acidic laundry detergent compositions

Also Published As

Publication number Publication date
FR1419437A (fr) 1965-11-26
NL6414208A (OSRAM) 1965-07-05
ES307775A1 (es) 1965-06-16
GB1089998A (en) 1967-11-08
DK120958B (da) 1971-08-09
DE1271885B (de) 1968-07-04
US3388069A (en) 1968-06-11
DE1299092B (de) 1969-07-10
GB1089997A (en) 1967-11-08
BE657865A (OSRAM) 1965-07-05
CH467721A (de) 1969-01-31

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