Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
  • C07C407/003—Separation; Purification; Stabilisation; Use of additives
  • C07C407/006—Stabilisation; Use of additives
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/15—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/17—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen in an inert solvent

Definitions

• the present invention relates to a process for producing'stable, aqueous solutionsof peroxybenzoic acid and substituted peroxybenzoic acids for use as bleaching agents.
• the bleach in the form of a dilute, aqueous solution to avoid localized bleach-ing and for ease in measuring and adding the varied amounts of bleach required with different garments and different Washing loads.
• Bleaching agents presently in use have been found to have serious drawbacks.
• sodium hypochlorite a commonly used bleach
• it causes measurable degradation of the fabric during bleaching and is capable of causing localized oven-bleaching by direct contact of the bleach with the fabric in the absence of water.
• active chlorine bleaching agents such as the chlorinated isocyanuric acids
• bleaches have been suggested to overcome the problem of fabric degradation, e.g. sodium perborate and potassium persulfates (Caroates).
• sodium perborate fabric degradation is reducd but the bleaching action is inferior to the prior sodium hypochlorite bleaches when conducted under conventional domestic Washing conditions.
• the potassium persulfate bleaches give improved bleaching action over sodium persulfate but are inferior to sodium hypochlorite.
• potassium persulfates are not stable in aqueous solutions, and therefore, cannot be supplied in the form of dilute, aqueous bleaching solutions.
• Peroxybenzoic acid and substituted peroxybenzoic acids give good bleaching action and do not degrade the bleached fabric but they have not been used as domestic laundry bleaching agents because of the poor stability of these compositions in solution and the inability to form stable, aqueous-based solutions thereof.
• peroxybenzoic acid and substituted peroxybenzoic acids which do not contain oxidizable groups can be made up into stable, aqueous-based bleaching solutions by dissolving these acids in a mixed solvent comprising water and tert-butyl alcohol, in which the tert-butyl alcohol is present in a weight ratio relative to the water of up to 1:1, but always in amounts sufficient to both dissolve and stabilize the peroxy acid and to form a homogeneous solution.
• tert-butyl alcohol can be used to make up stable, homogeneous, aqueous solutions of these non-oxidizable peroxybenzoic acids, particularly since these peroxy acids alone are virtually insoluble in water.
• U.S. Serial No. 119,325, filed on June 26, 1961 I have taught that certain tertiary alcohol solvents are capable of stabilizing peroxycarboxylic acids.
• the tertiary alcohol was used either alone as the entire solvent or mixed with small amounts (no more than 20% by weight.) of another organic solvent for the peroxycarboxylic acid.
• as little as 10% by Weight of the tertiary alcohol in a water solution has been found elfective in stabilizing the peroxycarboxylic acid.
• tertiary alcohol useful in the present invention is tert-butyl alcohol.
• the tert-butyl alcohol can be used to make up the aqueous-based solutions of the peroxybenzoic acids up to about 12% by weight when the alcohol is present in a 1:1 weight ratio with water. Lower amounts of the tert-butyl alcohol can be used to make up more dilute peroxy acid solutions.
• a dilute solution of about 2% by weight peroxy acid requires about 10% by weight of the tertiary alcohols to impart stability and homogeneity to the aqueous solution.
• the tertiary alcohols used in making up the aqueous bleach solution should be free of impurities that can cause rapid decompositon of the peroxybenzoic acids or which can be oxidized by these acids, thus wastefully consuming them.
• the most common offending impurities are heavy metals. Heavy metals initiate catalytic decomposition of the peroxybenzoic acids, and therefore, are highly undesirable, even in small amounts.
• Two methods can be employed to eliminate decomposition by heavy metals. The first of these is to remove the heavy metals by distilling the tertiary alcohols in glass or glass-lined equipment. Another is to render the heavy metals inactive by adding a small amount, on the order of about p.p.m., of a metal chelating agent.
• a compound such as dip-icolinic acid is an ideal chelating agent and effectively ties up the heavy metal in a complex organic structure, thereby making it unavailable for initiating decomposition of the peroxybenzoic acids.
• the peroxy acid which has been found most suitable in the present bleaching solution is peroxybenzoic acid because of its high solubility in the tert-butyl alcohol and because it has proportionately more active oxygen per molecular weight than do the substituted peroxybenzoic acids.
• Aqueous solutions having up to about 12% by weight of peroxybenzoic acid can be made up readily when tertbutyl alcohol is employed as the tertiary alcohol. In making up such solutions, they should contain about 44% by weight water, about 12% by weight peroxybenzoic acid, and from about 44% by weight tertbutyl alcohol.
• a preferred bleaching mixture contains from about 52% by weight water, about 9% peroxybenzoic acid, and 39% by weight of tert-butyl alcohol.
• substituted peroxybenzoic acids can be employed which do not contain groups that can be oxidized by the peroxybenzoic acids.
• Hydrogen Peroxide percent. Tert-butanol, percent- Distilled Water, percent Dipicolinic Acid, p.p.rn Peroxybenzoie Acid, percent--.. Hydrogen Peroxide, percent. Tcrt-butanol, percent. Distilled Water, percent Dipicolinic Acid, p.p.m.
• substituted peroxybenzoic acids further must be sufiiciently soluble in the tertiary alcohol-water mixture to reach the peroxy acid content desired.
• nitro groups are non-oxidizable, but they are unsuitable in the present application because the nitro group so lowers the solubility of the resultant peroxybenzoic acid that it cannot be used in making up the present bleach solutions.
• Substituted peroxybenzoic acids which contain chloro, lower saturated aliphatic, methoxy, and other such groups have been found suitable.
• Peroxy-benzoic acid and substituted peroxybenzoic acids have negligible rates of hydrolysis in water solutions and therefore, are effective in retaining their active oxygen contents for a sustained period in aqueous solutions.
• the present aqueous-based peroxybenzoic acid solutions have been found to have high germicidal action. This is advantageous because the bleaching agent effectively sterilizes the soiled garments it contacts during conventional domestic laundering.
• the present aqueous solutions can be used as germicidal and disinfecting solutions because of their high germicidal action. The makeup of these germicides in an aqueous base facilitates their use and permits sterilization of equipment without residual organic solvents being retained thereon.
• EXAMPLE 1 Peroxybenzoic acid was dissolved in tert-butyl alcohol and this solution was mixed with various proportions of distilled water. To these solutions were added small amounts of dipicolinic acid to act as sequestering agents 10 for the removal of heavy metal ion impurities. The samples were stored at room temperature (about C.) for up to 6 months and were analyzed periodically for their peroxy acid and hydrogen peroxide content by the method described in Analytical Chemistry, 20 (1948),
• the amount of hydrogen peroxide in the sample indicates the degree of hydrolysis of the peroxybenzoic acid in accordance with the formula set forth below:
• EXAMPLE 2 The peroxybenzoic acid solution identified as Sample 1 in Example 1, after storage for 6 months at room temperature, and which contained 11.04% by weight of peroxybenzoic acid, was tested for germicidal activity against Staphylococcus aureus by the standard procedure for phenol coefficient determination as described in Official Methods of Analyses of the A.O.A.C., published by A.O.A.C. (1960), pp. 63-65. The phenol coefficient was found to be 400, calculated on the basis of the active ingredient. An acceptable, active germicide should have a phenol coefficient of about 200.
• EXAMPLE 3 The peroxybenzoic acid solution identified as Sample 1 in Example 1, after storage for 6 months at room temperature, and which contained 11.04% by weight of peroxybenzoic acid, was tested for bleaching effectiveness.
• the procedure used was as follows: Thirty-two cotton" swatches (5" x 5" desized cotton Indianhead fabric, uniform in weave and thread count) were stained with tea, coffee and wine in the following manner: Five tea bags were placed in a liter of water and boiled for 5 minutes. Thereafter, the swatches were immersed in tea and the boiling continued for 5 minutes. Thirty-two additional swatches of the same cloth were coffee-stained by boiling 50 g.
• the pH of the solutions were adjusted to 9.5, using soda ash. Cut-up pieces of white terry cloth toweling were then added to provide a typical household wash 'water/ cloth ratio of 20:1.
• the Terg-O-Tometer was then operated at 72 cycles per minute for 15 minutes at a temperature of 120 F. At the end of the wash cycle, the swatches were removed, rinsed under cold tap water and dried in a Proctor-Schwartz skeiu'dryer. The tests Were run in triplicate and included detergent blanks. Reflectance readings of the swatches were then taken before and after the wash cycle wth a Reflectometer and the readings were averaged. The percent stain removal was obtained in accordance with the following formula:
• Meta-chloroperoxybenzoic'acid was dissolved in tertbutyl alcohol and this solution was mixed with various proportions of distilled Water. To these solutions were added small amounts of dipicolinic acid to act as sequestering agents for the removal of heavy metal ion impurities. The samples were stored at room temperature (about 25 C.) for up to 6 months and were analyzed periodically for their peroxy acid and hydrogen peroxide content by the method described in Analytical Chemistry, 20 (1948), p. 1061. The concentration of the ingredients in the solution and the results of the analysis are listed in Table III below:
• a stable, aqueous based composition which consists percent. Hydrogen Peroxide, percent... Tert-butanol, percent. Distilled Water, percent Dipicolinic Acid, p.p.m Meta-chloroperoxybenzoic Acid,
• the amount of hydrogen peroxide in the sample indicates the degree of hydrolysis of the metachloroperoxybenzoic acid.
• a peroxybenzoic acid essentially of a peroxybenzoic acid, said acid being free of groups which can be oxidized by peroxycar-boxylic acids, dissolved in a mixed solvent consisting essentially of Water and tert-butyl alcohol, in which the tert-butyl alcohol is present in weight ratios relative to the water of up to 1:1, and in amounts sufiicient to form a homogeneous solution.
• composition of claim 1 in which the peroxybenzoic acid is present in amounts of from about 2% to about 12% by weight of the solution.
• a stable, aqueous-based composition consisting essentially of peroxybenzoic acid dissolved in a mixed solvent consisting essentially of water and tert-butyl alcohol, in which the tertbutyl alcohol is present in weight ratios relative to water of up to 1:1, and in amounts sufiicicnt to form a homogeneous solution.
• composition of claim 3 in which the peroxybenzoic acid is present in amounts of from about 2% to about 12% by weight.
• a stable, aqueous-based composition consisting es- .sentially of meta-chloroperoxybenzoic acid dissolved in References Cited by the Examiner UNITED STATES PATENTS 3,075,921 1/1963 Brocklehurst et a1. 25299 3,130,169 4/1964 Blumbergs et a1. 252-l86 3,144,297 8/1964 Kinder 252-104 XR JULIUS GREENWALD, Primary Examiner.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (3)

• 1964
  • 1964-04-06 US US357765A patent/US3248336A/en not_active Expired - Lifetime
• 1965
  • 1965-03-22 FI FI0696/65A patent/FI43586B/fi active
  • 1965-03-26 NL NL6503875A patent/NL6503875A/xx unknown
  • 1965-03-30 ES ES0311236A patent/ES311236A1/es not_active Expired
  • 1965-03-31 BE BE661881A patent/BE661881A/xx unknown
  • 1965-04-02 GB GB13981/65A patent/GB1049190A/en not_active Expired
  • 1965-04-06 DE DEF45743A patent/DE1289815B/de active Pending

Patent Citations (3)

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