US3049495A - Peroxymonosulfate-diethylenetriamine pentaacetic acid composition - Google Patents

Peroxymonosulfate-diethylenetriamine pentaacetic acid composition Download PDF

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Publication number
US3049495A
US3049495A US824175A US82417559A US3049495A US 3049495 A US3049495 A US 3049495A US 824175 A US824175 A US 824175A US 82417559 A US82417559 A US 82417559A US 3049495 A US3049495 A US 3049495A
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US
United States
Prior art keywords
peroxymonosulfate
dtpa
manganese
bleaching
pentaacetic acid
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
Application number
US824175A
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English (en)
Inventor
Gordon I Jenkins
Elbert V Kring
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to BE590477D priority Critical patent/BE590477A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US824175A priority patent/US3049495A/en
Priority to GB9704/60A priority patent/GB889079A/en
Priority to FR825965A priority patent/FR1255860A/fr
Application granted granted Critical
Publication of US3049495A publication Critical patent/US3049495A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937Stabilising agents
    • C11D3/394Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds

Definitions

  • This invention relates to solid bleaching and cleansing compositions containing a peroxymonosulfate compound which can be effectively employed in practically any common tap water. More particularly, this invention relates to solid bleaching and cleansing compositions containing a novel combination of a peroxymonosulfate compound and a sequestering agent.
  • peroxymonosulfate compounds containing HSO such as NaHS and K50 are highly eifective bleaching compounds, being stronger oxidizing agents than hydrogen peroxide and many other commonly used per compounds.
  • HSO such as NaHS and K50
  • the use of such strong oxidizing agents in common tap water presents a problem because some tap water supplies contain manganese in amounts of about 0.1 ppm. or more. Analysis has shown that ordinary tap water rarely contains more than 0.2 p.p.m. manganese. Under the influence of peroxymonosulfates the manganese becomes oxidized to a high valence state (+3 or +4) and imparts a yellow discoloration to the object being treated. The problem especially acute when white cloth is laundered or white porcelain is cleansed. Tests have shown that as little a 0.1 p.p.m. manganese in the water will noticeably discolor White cloth or porcelain when manganese is oxidized to a higher valence state.
  • manganese ions can be eifeo tively sequestered from the oxidizing action of peroxymonosulfate with diethylenetriamine pentaacetic acid (DTPA) or the alkali metal salts thereof and that these sequestering agents are not attacked by peroxymonosulfate to an appreciable extent. It has also been found that DTPA does not decompose peroxymonosulfate to any appreciable extent. Additionally, it has been determined that the monopersulfate compound and DTPA may be formulated in solid bleaching and cleansing compositions which can be added to common tap water containing substantial amounts of manganese with the result that the latter is effectively sequestered so that it will not discolor the substrate being bleached.
  • DTPA diethylenetriamine pentaacetic acid
  • Oxone refers to a mixture of KHSO KHSO4 and K in mole proportions of 2/ 1/1, and KHSO the active oxygen source, constitutes about 50% by weight of the mixture.
  • the cloth was given a thorough rinse after washing and then dried. After the wash and dry cycle, the reflectances of the swatches were determined in a Hunter multipurpose refiectometer using a blue filter, the fall in reflectance representing a measure of the yellowing of the fabric. The results show that even small concentrations (about 011 ppm.) of manganese are oxidized and cause yellowing.
  • Example 1 The same bleaching formulation containing DTPA, a white powder commercially available as Perma-Kleer 140, Refined Products Corporation, was employed under the same conditions as noted above in an amount equal to about 6% by weight based on potassium peroxymonosulfate content and the DTPA was mixed in the formulation prior to use.
  • the water was common tap water containing about 0.2 p.p.rn. manganese. The discoloration that resulted from yellowing under identical conditions when DTPA was not added is also shown. It is to be noted that the use of DTPA caused no significant decomposition of the peroxy-monosulfate ions as indicated by active oxygen analysis.
  • Example 2 This example illustrates the effect of DTPA when used in a cleanser.
  • a use-worn sink was scoured with the following cleanser:
  • the cleaning was carried out using tap water containing approximately 0.3 p.p.m. manganese and the cleaned portion of the sink was allowed to stand in Water for 15 minutes between each cleaning treatment. After 8 washes a distinct yellow discoloration was apparent. On a separate section of the same sink the above formulation containing 6% DTPA (based on the weight of potassium peroxymonosulfate, the preferred source of active oxygen) was used. After 8 washes there was no visible discoloration.
  • the alkali metal salts of the acid are equivalents and are also excellent sequestrants for manganese.
  • sodium or potassium may be substituted in any or all of the five carboxyl groups of DTPA as noted in Example 3.
  • the structures of DTPA and DTPA-5 Na are as follows:
  • the compositions specifically set forth above are representative and should not be construed to be limiting. Ordinarily, these formulations are used in alkaline solutions. However, peroxymonosulfates in combination with DTPA can be used in either acid or alkaline solutions.
  • this combination can be used as a bleaching composition alone.
  • the amount of active oxygen supplied by the peroxymonosulfate will vary from about 5 to 600 p.p.m. Throughout the specification, percentages and parts are calculated on a weight basis unless otherwise designated.
  • solid bleaching compositions H and cleansers that contain an alkali metal peroxymonosulfate and DTPA and its equivalents may be added to practically any tap water without discoloring the object being treated.
  • the amount of DTPA and its equivalents must be at least 0.01 part by weight based on each part of alkali metal peroxymonosulfate content; preferred compositions contain 0.02-0.1 part of the former to each part of the latter, although there is no critical upper limit to the amount of the sequestrant used.
  • compositions of the present invention are stable under normal storage conditions. Contributing to the uniqueness of compositions containing the two ingredients is the fact that upon the addition of Water, neither ingredient is antagonistic to the other, and th sequestrant operates rapidly to prevent the peroxymonosulfate from oxidizing manganese. These conditions prevail throughout the relatively short time required for bleaching and cleansing.
  • the sequestrant To be efiective, it is essential that the sequestrant have all of the desirable characteristics in solution for at least a relatively short period of time under household conditions.
  • the outstanding sequestrant for this use is diethylenetriamine pentaacetic acid and alkali metal salts thereof.
  • Other agents which theoretically should sequester manganese have been found to be much less eifective.
  • a composition consisting essentially of an alkali metal peroxymonosulfate and a compound selected from the group consisting of diethyienetriamine pentaacetic acid and alkali metal salts thereof, at least 0.01 part by Weight of said last named compound being present for each part by weight of said peroxymonosulfate.
  • a composition consisting essentially of potassium peroxymonosulfate and diethylenetriamine pentaacetic acid, at least 0.01 part by weight of said acid being present for each part by weight of said peroxymonosulfate.
  • composition consisting essentially of 1 part 'by 15 P June 1953, 67106-1500- Weight of potassium peroxymonosulfate and 0.02 to 0.1 part by weight of diethylenetriamine pentaacetic acid.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US824175A 1959-07-01 1959-07-01 Peroxymonosulfate-diethylenetriamine pentaacetic acid composition Expired - Lifetime US3049495A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE590477D BE590477A (sv) 1959-07-01
US824175A US3049495A (en) 1959-07-01 1959-07-01 Peroxymonosulfate-diethylenetriamine pentaacetic acid composition
GB9704/60A GB889079A (en) 1959-07-01 1960-03-18 Improvements relating to bleaching and cleansing compositions
FR825965A FR1255860A (fr) 1959-07-01 1960-05-02 Procédé de fabrication de compositions solides de blanchiment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US824175A US3049495A (en) 1959-07-01 1959-07-01 Peroxymonosulfate-diethylenetriamine pentaacetic acid composition

Publications (1)

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US3049495A true US3049495A (en) 1962-08-14

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US (1) US3049495A (sv)
BE (1) BE590477A (sv)
GB (1) GB889079A (sv)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3303104A (en) * 1963-12-12 1967-02-07 Lever Brothers Ltd Compositions containing discoloration inhibitors
US3330766A (en) * 1963-11-08 1967-07-11 Lever Brothers Ltd Discoloration inhibitors
WO1994003553A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxy bleaching composition stabilized with ethylenediamine-n,n'-disuccinic acid
US5559089A (en) * 1992-03-12 1996-09-24 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
US5599781A (en) * 1995-07-27 1997-02-04 Haeggberg; Donna J. Automatic dishwashing detergent having bleach system comprising monopersulfate, cationic bleach activator and perborate or percarbonate
US5718837A (en) * 1993-03-12 1998-02-17 Fmc Corporation Persulfate mixtures for repulping wet strength paper
US5830382A (en) * 1993-08-17 1998-11-03 Fmc Corporation Persulfate/metal mixtures for repulping and/or decolorizing paper
US5888350A (en) * 1993-08-17 1999-03-30 Fmc Corporation Method for repulping and/or decolorizing broke using persulfate/metal mixtures

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2311314A (en) * 1940-09-20 1943-02-16 Du Pont Purification of water
US2886534A (en) * 1954-12-23 1959-05-12 Du Pont Production of alkali metal monopersulfates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2311314A (en) * 1940-09-20 1943-02-16 Du Pont Purification of water
US2886534A (en) * 1954-12-23 1959-05-12 Du Pont Production of alkali metal monopersulfates

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330766A (en) * 1963-11-08 1967-07-11 Lever Brothers Ltd Discoloration inhibitors
US3303104A (en) * 1963-12-12 1967-02-07 Lever Brothers Ltd Compositions containing discoloration inhibitors
US5559089A (en) * 1992-03-12 1996-09-24 The Procter & Gamble Company Low-dosage automatic dishwashing detergent with monopersulfate and enzymes
WO1994003553A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxy bleaching composition stabilized with ethylenediamine-n,n'-disuccinic acid
US5718837A (en) * 1993-03-12 1998-02-17 Fmc Corporation Persulfate mixtures for repulping wet strength paper
US5972164A (en) * 1993-03-12 1999-10-26 Fmc Corporation Persulfate mixtures for repulping wet strength paper
US5830382A (en) * 1993-08-17 1998-11-03 Fmc Corporation Persulfate/metal mixtures for repulping and/or decolorizing paper
US5888350A (en) * 1993-08-17 1999-03-30 Fmc Corporation Method for repulping and/or decolorizing broke using persulfate/metal mixtures
US5599781A (en) * 1995-07-27 1997-02-04 Haeggberg; Donna J. Automatic dishwashing detergent having bleach system comprising monopersulfate, cationic bleach activator and perborate or percarbonate

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Publication number Publication date
GB889079A (en) 1962-02-07
BE590477A (sv)

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