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
  • C11D3/3945—Organic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

• Peroxybenzoic acid has been known and used for a long time as an oxidizing agent in preparative and analytical chemistry. Unfortunately, peroxybenzoic acid possesses poor stability, decomposing at the approximate rate of 10% per week at room temperature even when maintained in an isolated state. Undoubtedly due largely to this drawback, it has not been found practicable to utilize peroxybenzoic acid as an industrial oxidizing agent, for example as an industrial bleaching agent. This is particularly unfortunate since peroxybenzoic acid is potentially an excellent bleaching agent and markedly superior to sodium perborate which is a bleaching agent normally used in household washing preparations. Thus peroxybenzoic acid in alkaline solution bleaches tea stained cloth in five minutes at 130 F. to an extent which is only to be achieved in ten minutes at the boil using alkaline hydrogen peroxide of equivalent available oxygen content.
• a solid detergent composition comprising an active detergent ingredient and a peroxybenzoic acid which is substituted in the benzene nucleus by at least one group selected from nitro-, chloro-, cyano-, lower alkyland lower alkoxy-groups, the substitution being such that the substituted peroxybenzoic acid has a melting point not lower than 50 C.
• Table I is illustrative of the melting points, stability and bleaching effects using various substituents.
• the percentage colour removal obtained by sodium perborate used under the same conditions at the same available oxygen content in the bleach bath was 4%.
• the available oxygen content is determined as follows:
• 0.05 gm. of the peroxyacid is weighed into a 250 ml. conical flask and 10 ml. of dioxane is added.
• 10 ml. glacial acetic acid When the pcroxyacid is completely dissolved 10 ml. glacial acetic acid and 10 ml. of 10% aqueous potassium iodide solution are added followed by 50 ml. distilled water.
• the iodine is titrated with 0.025 N sodium thiosulphate solution using thyodene indicator near the end point.
• the bleaching power of the peroxyacids is determined by adding sufficient of the peroxyacid to a 0.5% aqueous solution of a commercial heavy-duty synthetic detergent composition containing no other bleaching agent to give an available oxygen content of the solution of 50 parts per million.
• the pH is adjusted to 9.0 by addition of caustic soda or sulphuric acid as necessary.
• a 2-inch square of tea-stained cotton is agitated in this solution for 5 minutes at F. and is then rinsed and dried.
• the reflectance of the cloth is measured by an EEL Reflectance Spectrophotometer.
• the percentage colour removal is reflectance of bleached cloth minus reflectance of stained cloth divided by reflectance of desized cloth minus reflectance of stained cloth, and multiplied by 100.
• a tea solution is prepared byboiling 28 gm. tea in 1 litre distilled water under reflux for one hour and then filtering the solution.
• a piece of desized cotton cloth, 2 feet x 3 feet, is boiled in this filtered solution for one hour and is then rinsed with 3 cold distilled water until no more colour can be removed and finally dried.
• Table I shows that the substituted peroxybenzoic acids with higher melting points have greater stability than those with lower melting points. It is clear that those compounds with melting points above 50 C. are sufficiently stable to be of value as bleaching agents in commercial solid detergent products while those with melting point below 50 C. are too unstable to be of value commercially.
• peroxyacids are effective bleaching agents in the temperature range 100-175 F., they are eminently suitable for use in textile washing operations such as are carried out in domestic washing machines.
• the detergent compositions of the invention may contain as active detergent ingredient, soap and/or synthetic detergents. Particularly suitable are anionic synthetic detergents such as alkyl benzene sulphonates,'alkyl sulphates, fatty acyl isethionates and fatty acyl taurides.
• anionic synthetic detergents such as alkyl benzene sulphonates,'alkyl sulphates, fatty acyl isethionates and fatty acyl taurides.
• the compositions may also contain the customary alkaline builder salts such as pyrophosphates, tripolyphosphates and the normal additives such as solid suspending agents (e.g.
• Such detergent compositions for household washing purposes are generally alkaline, and the incorporation therein of the substituted peroxybenzoic acid is liable to impair the stability of the substituted peroxybenzoic acid. This can be largely overcome by pelletizi-ng the substituted peroxybenzoic acid alone or in admixture with an inorganic neutral or acid salt so as to give pellets of, say, A" diameter. This considerably reduces the relative area of contact between the substituted peroxybenzoic acid and the other ingredients of the washing composition and so renders the substituted peroxy-compound more immune against loss of stability. Moreover, the substituted peroxybenzoic acid may be protected from contact with the other ingredients of the mixture by coating it, preferably in pellet form, with an inert protective material which is removed by solution or melting when the Washing composition is used in normal washing operations.
• an inert protective material which is removed by solution or melting when the Washing composition is used in normal washing operations.
• a suitable protective material is parafiin wax of iodine value (I.V.) 10 or less, and melting point below about 120 F.
• Table II below shows the-improvement of stability of 2,4-dichloroperoxybenzoic acid (DC PBA) in a heavy duty synthetic detergent composition which is achieved by pelletizing it, with or without subsequent coating, before mixing with the detergent powder.
• the table shows the percentage decomposition of the DCPBA, as measured by loss of available oxygen, in detergent powder when stored for three months at 70 F. in a carton.
• silicate content of the detergent powder was replaced by sodium sulphate.
• the pellets contained by weight DCPBAand 50% by weight inorganic salt.
• the weight ratio of wax i r to pellet was 0.25:1.
• the wax used had I.V. l0 and melting point -1l0 F.
• Peroxybenzoic acid itself may be prepared by reacting dibenzoyl peroxide with sodium methoxide under anhydrous conditions at low temperature (below 0 C.) followed by acidification according to the chemical equation:
• the nuclear substituted peroxybenzoic acids are obtainable by the same procedure, using the appropriately substituted dibenzoyl peroxides.
• Table III are given the starting materials and yields in thus preparing substituted peroxybenzoic acids.
• the substituted dibenzoyl peroxides, used as starting materials, are obtainable from the appropriately substituted benzoyl chloride by the method of Swain, Stockmayer and Clarke (J. Amer. Chem. Soc. 72, 5426 1950)
• the substituted peroxybenzoic acids may be purified by recrystallisation from chloroform or by sublimation.
• the mother liquor was diluted with an equal volume of petroleum ether (boiling point 40-60" C.), cooled to -80C., filtered rapidly and the crystals dried in a vacuum desiccator to give a purity of 98.1%.
• peroxyacids which can be purified by the same technique are 4-nitro-, 4-chloro and 4-methyl-peroxybenzoic acids.
• a water-soluble detergent composition consisting essentially of a solid active anionic synthetic detergent ingredient which is present in sufficient amount to remove soil from textile materials, said solid active anionic synthetic detergent ingredient being selected from the group consisting of alkyl benzene sulphonates, alkyl sul phates, fatty acyl isethionates and fatty acyl taurides; and, a solid substituted peroxybenzoic acid bleaching agent which is present in suflicient amount to provide bleaching activity and is characterized by a stability to de composition in its solid state, said peroxybenzoic acid bleaching agent being substituted in the benzene nucleus by at least one radical selected from the group consisting of nitro, chloro, cyano, lower alkyl and lower alkoxy radicals, the substitution being such that the substituted peroxybenzoic acid bleaching agent has a melting point of at least 50 C.
• a water-soluble detergent composition consisting essentially of a solid active anionic synthetic detergent ingredient which is present in sufiicient amount to remove soil from textile materials, said solid active anionic synthetic detergent ingredient being selected from the group consisting of alkyl benzene sulphonates, alkyl sulphates, fatty acyl isethionates and fatty acyl taurides; and, a solid substituted peroxybenzoic acid bleaching agent which is present in sufficient amount to provide bleaching activity and is characterized by a melting point of at least 50 C.
• peroxybenzoic acid bleaching agent being selected from the group consisting of 2-chloro-, 3- chloro-, 4-chloro-, 2,4-dichloro-, 2-nitro-, 3-nitro-, 4-nitro-, 3-methyl-, 4-methyl-, 4-methoxy-, 4-tertiary butyl-, 4isopropyl-, 4-cyano-, and 2-chloro-4-nitroperoxybenzoic acids.
• a water-soluble detergent composition consisting essentially of a solid active anionic synthetic detergent ingredient which is present in suflicient amount to remove soil from textile materials, said solid active anionic synthetic detergent ingredient being selected from the group consisting of alkyl benzene sulphonates, alkyl sulphates, fatty acyl isethionates and fatty acyl taurides; and, a solid substituted peroxybenzoic acid bleaching agent which is present in suflicient amount to provide bleaching activity and is characterized by a melting point of at least 50 C. and a stability to decomposition in its solid state, said peroxybenzoic acid bleaching agent being 2,4-dichloroperoxybenzoic acid.
• an inorganic non-alkaline salt selected from the group consisting of ammonium sulphate, sodium sulphate, sodium hydrogen sulphate, and disodium dihydrogen pyrophosphate
• a water-soluble detergent composition consisting essentially of (a) a detergent ingredient for removing soil from textile materials, said detergent ingredient consisting essentially of 23% by weight sodium dodecyl benzene sulphonate 39% by weight sodium tripolyphosphate 7% by weight silicate solids 1% by weight sodium carboxymethyl cellulose 19% by weight sodium sulfate 3% by weight coconut monoethanolamide 8% by weight water, and

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• Inorganic Chemistry (AREA)
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Cited By (23)

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Citations (3)

• 0
  • BE BE587389D patent/BE587389A/xx unknown
  • NL NL248201D patent/NL248201A/xx unknown
• 1959
  • 1959-02-11 GB GB4843/59A patent/GB886188A/en not_active Expired
• 1960
  • 1960-01-30 DE DEH38542A patent/DE1105092B/de active Pending
  • 1960-02-03 US US6379A patent/US3075921A/en not_active Expired - Lifetime
  • 1960-02-05 FR FR817740A patent/FR1247242A/fr not_active Expired
  • 1960-02-11 CH CH153360A patent/CH390442A/fr unknown

Patent Citations (3)

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